Grease compositions having polyurea thickeners made with isocyanate terminated prepolymers

ABSTRACT

This disclosure relates to grease compositions having at least one base oil, and at least one polyurea thickener. The at least one polyurea thickener is prepared by reacting an isocyanate-terminated prepolymer with at least one amine under reaction conditions sufficient to prepare the at least one polyurea thickener. The isocyanate-terminated prepolymer is prepared by reacting a polyisocyanate with a polyol, at an NCO/OH equivalent ratio of 1.05:1 to 10:1, under reaction conditions sufficient to prepare said isocyanate-terminated prepolymer. When the grease compositions are used under high temperature conditions, structural stability and resistance to breaking down in accordance with DIN 51821 (FAG FE9) is improved. This disclosure also relates to a method of preparing the grease compositions. This disclosure further relates to a method for improving high temperature performance of a grease composition in a mechanical component lubricated with the grease composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 62/781,745 filed Dec. 19, 2018, which is herein incorporated byreference in its entirety.

FIELD

This disclosure relates generally to lubricating compositions andmethods of making and using the same. More specifically, the presentdisclosure relates to grease compositions having polyurea thickenersmade with isocyanate-terminated prepolymers. The grease compositionsexhibit minimal age hardening over time, and improved mechanicalstability in high temperature environments. The grease compositionsprovide optimum performance in a wide variety of diverse industrial andautomotive applications.

BACKGROUND

Lubricating formulations and greases with a wide assortment of differentmaterials are known. For example, polyurea greases are known and can bemade from any of a wide variety of base stocks of lubricating oilviscosity, as well as mixtures of base stocks. Greases have variedlevels of desirable grease characteristics, such as dropping point,penetration, mechanical stability, shear stability, oxidationresistance, high temperature resistance, etc., based on its composition.The above characteristics are used to describe the lubricating life of aparticular grease.

High temperature resistance is a property desirable in grease for manyindustrial and automotive applications. The exposure to hightemperatures accelerates the breakdown process of grease compositions.

From the 1970s to date, the commercial use of isocyanates in themanufacturing of grease thickeners has been primarily in the form of(4,4′-methylene diphenyl diisocyante (MDI) and toluene-2,4-diisocyanate(TDI) or isomeric mixtures of the individual compounds. Polyurea greasedevelopment has been directed mainly to improvements to constantvelocity (CV) joint greases formulated with low frictioncharacteristics. The literature describes conventional thickener typesusing exclusively TDI or MDI as the isocyanate reacting with aromatic,alicyclic and aliphatic amines. Contributions to most polyurea greasethickeners, as disclosed in the literature, are either made byadditives, additive combinations, specific oil or oil blends.

As technology advances and throughput increases with mechanical devices,there is an increased demand for higher temperature operating conditionsand lubricating compositions, such as grease, with enhanced resistance.For example, industrial and automotive greases operate in hightemperature environments. The working life of grease is limited in suchan environment, which results in greater wear on the equipment andlonger downtimes as a result of maintenance (e.g., re-greasing the ballbearings and replacement/maintenance of warn parts of the equipment).

Thus, a need exists for lubricating greases that have enhanced/extendedhigh temperature resistance that can be utilized in high temperatureenvironments.

SUMMARY

This disclosure relates generally to lubricating compositions andmethods of making and using the same. More specifically, the presentdisclosure relates to grease compositions having polyurea thickenersmade with isocyanate-terminated prepolymers. The grease compositionsexhibit minimal age hardening over time, and improved mechanicalstability in high temperature environments. The grease compositionsprovide optimum performance in a wide variety of diverse industrial andautomotive applications.

This disclosure relates in part to grease compositions having at leastone base oil, and at least one polyurea thickener. The at least onepolyurea thickener is prepared by reacting an isocyanate-terminatedprepolymer with at least one amine under reaction conditions sufficientto prepare the at least one polyurea thickener. Theisocyanate-terminated prepolymer is prepared by reacting apolyisocyanate with a polyol, at an NCO/OH equivalent ratio of about1.05:1 to about 10:1, under reaction conditions sufficient to preparethe isocyanate-terminated prepolymer.

When a grease composition having a polyurea thickener of this disclosureis used under high temperature conditions, high temperature performancein accordance with DIN 51821 (FAG FE9) is improved, as compared to hightemperature performance achieved using a grease composition containingother than the polyurea thickener of this disclosure.

When a polyurea grease composition having a polyurea thickener of thisdisclosure is used in high temperature conditions, structural stabilityand resistance to breaking down is improved in accordance with DIN 51821(FAG FE9), as compared to structural stability and resistance tobreaking down achieved using a grease composition containing other thanthe polyurea thickener of this disclosure.

When a polyurea grease composition having a polyurea thickener of thisdisclosure is tested for frictional properties using a Mini-TractionMachine (MTM) at 100° C., 1.0 GPa, 50% slide/roll ratio (SRR), and 3.0m/s-0 m/s, coefficient of friction is improved, as compared tocoefficient of friction achieved using a grease composition containingother than the polyurea thickener of this disclosure.

This disclosure further relates in part to a method of preparing agrease composition comprising mixing at least one base oil, and at leastone polyurea thickener. The at least one polyurea thickener is preparedby reacting an isocyanate-terminated prepolymer with at least one amineunder reaction conditions sufficient to prepare said at least onepolyurea thickener. The isocyanate-terminated prepolymer is prepared byreacting a polyisocyanate with a polyol, at an NCO/OH equivalent ratioof about 1.05:1 to about 10:1, under reaction conditions sufficient toprepare the isocyanate-terminated prepolymer.

This disclosure yet further relates in part to a method for improvinghigh temperature performance of a grease composition in a mechanicalcomponent lubricated with the grease composition. The method involvesusing a grease composition comprising: at least one base oil, and atleast one polyurea thickener. The at least one polyurea thickener isprepared by reacting an isocyanate-terminated prepolymer with at leastone amine under reaction conditions sufficient to prepare said at leastone polyurea thickener. The isocyanate-terminated prepolymer is preparedby reacting a polyisocyanate with a polyol, at an NCO/OH equivalentratio of about 1.05:1 to about 10:1, under reaction conditionssufficient to prepare the isocyanate-terminated prepolymer.

It has been surprisingly found that, when a grease composition having apolyurea thickener of this disclosure is used under high temperatureconditions, high temperature performance in accordance with DIN 51821(FAG FE9) is improved, as compared to high temperature performanceachieved using a grease composition containing other than a polyureathickener of this disclosure, in particular, a commercial polyureathickened grease composition formulated with the same oil and additivepackage.

Also, it has been surprisingly found that, in accordance with thisdisclosure, structural stability and resistance to breaking down of agrease composition having a polyurea thickener of this disclosure isimproved when tested under high temperature conditions in accordancewith DIN 51821 (FAG FE9), as compared to structural stability andresistance to breaking down achieved using a grease compositioncontaining other than a polyurea thickener of this disclosure.

Further, it has been surprisingly found that, in accordance with thisdisclosure, when a grease composition having a polyurea thickener ofthis disclosure is tested using a Mini-Traction Machine (MTM) at 100°C., 1.0 GPa, 50% slide/roll ratio (SRR), and 3.0 m/s-0 m/s, coefficientof friction is improved, as compared to coefficient of friction achievedusing a grease composition containing other than a polyurea thickener ofthis disclosure.

Other objects and advantages of the present disclosure will becomeapparent from the detailed description that follows.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows first stage formulations including base oil weight percent,thickener weight percent and isocyanate:amine ratio, in accordance withthe Examples.

FIG. 2 shows test results for the first stage formulations includingworked penetration in accordance with ASTM D217-17, shell roll inaccordance with ASTM D1403, and dropping point in accordance with ASTMD2265, in accordance with the Examples.

FIG. 3 graphically shows worked penetration test results for the secondstage formulations in accordance with ASTM D217-17, in accordance withthe Examples.

FIG. 4 graphically shows shell roll test results for the second stageformulations in accordance with ASTM D1403, in accordance with theExamples.

FIG. 5 graphically shows dropping point test results for the secondstage formulations in accordance with ASTM D2265, in accordance with theExamples.

FIG. 6 graphically shows a Stribeck analysis for the grease formulationcontaining thickener Part A 5030 plus Part B 5030, blend 50/50, inaccordance with the Examples.

FIG. 7 graphically shows a Stribeck analysis for the grease formulationcontaining thickener Part A 5030 plus Part B MP 102, blend 50/50, inaccordance with the Examples.

FIG. 8 graphically shows a Stribeck analysis for the grease formulationcontaining thickener Part A MP 102 plus Part B MP 102, blend 50/50, inaccordance with the Examples.

FIG. 9 graphically shows a Stribeck analysis for the grease formulationcontaining thickener Part A MP 102 plus Part B 5030, blend 50/50, inaccordance with the Examples.

FIG. 10 graphically shows a Stribeck analysis for the commercial greaseformulation Polyrex EM, in accordance with the Examples.

FIG. 11 shows high temperature properties for the second stageformulations in accordance with the DIN 51821 (FAG FE9) test method, inaccordance with the Examples.

DETAILED DESCRIPTION

All numerical values within the detailed description and the claimsherein are modified by “about” or “approximately” the indicated value,and take into account experimental error and variations that would beexpected by a person having ordinary skill in the art. The phrase “majoramount” as it relates to components included within the greases of thespecification and the claims means greater than or equal to 50 wt. %, orgreater than or equal to 60 wt. %, or greater than or equal to 70 wt. %,or greater than or equal to 80 wt. %, or greater than or equal to 90 wt.% based on the total weight of the grease composition. The phrase “minoramount” as it relates to components included within the greases of thespecification and the claims means less than 50 wt. %, or less than orequal to 40 wt. %, or less than or equal to 30 wt. %, or greater than orequal to 20 wt. %, or less than or equal to 10 wt. %, or less than orequal to 5 wt. %, or less than or equal to 2 wt. %, or less than orequal to 1 wt. %, based on the total weight of the grease composition.The phrase “essentially free” as it relates to components includedwithin the greases of the specification and the claims means that theparticular component is at 0 weight % within the grease composition, oralternatively is at impurity type levels within the lubricating oil(less than 100 ppm, or less than 20 ppm, or less than 10 ppm, or lessthan 1 ppm).

The unique grease compositions of this disclosure relate in part togreases containing at least one polyurea thickener. The at least onepolyurea thickener is prepared by reacting an isocyanate-terminatedprepolymer with at least one amine under reaction conditions sufficientto prepare the at least one polyurea thickener. Theisocyanate-terminated prepolymer is prepared by reacting apolyisocyanate with a polyol, at an NCO/OH equivalent ratio of about1.05:1 to about 10:1, under reaction conditions sufficient to preparethe isocyanate-terminated prepolymer.

This disclosure relates in part to grease compositions with enhancedproperties that allow the grease to have improved structural stabilityand resistance to breaking down and losing its consistency under theeffect of high temperature conditions. In particular, this disclosuredescribes grease compositions that can allow grease longer lubricatinglife in hot environments such as steel mills and paper mills as well asimprove lubricating properties of grease. More specifically, it has beendiscovered that the use of polyurea greases containing at least onepolyurea thickener prepared from the reaction of anisocyanate-terminated prepolymer with at least one amine, surprisinglyprovide improved structural stability under high temperature conditions.

The present disclosure expands the applicability of greases in hightemperature environments as typically found in paper mills and steelmills roller bearings. In accordance with this disclosure, the abilityof the grease to maintain its structure and consistency even after useat high temperature is enhanced with the inclusion of at least onepolyurea thickener prepared from the reaction of anisocyanate-terminated prepolymer with at least one amine.

The polyurea grease compositions of this disclosure contain at least onepolyurea thickener that is prepared by reacting an isocyanate-terminatedprepolymer with at least one amine. The isocyanate-terminated prepolymeris prepared by reacting a polyisocyanate with a polyol, at an NCO/OHequivalent ratio of about 1.05:1 to about 10:1, or about 1.25:1 to about10:1, or about 1.5:1 to about 10:1, or about 1.75:1 to about 10:1, orabout 2:1 to about 10:1, or about 2.25:1 to about 10:1, or about 2.5:1to about 10:1, or about 2.75:1 to about 10:1, or about 3:1 to about10:1, or about 3.25:1 to about 10:1, or about 3.5:1 to about 10:1, orabout 3.75:1 to about 10:1, or about 4:1 to about 10:1, or about 4.25:1to about 10:1, or about 4.5:1 to about 10:1, or about 4.75:1 to about10:1, or about 5:1 to about 10:1, or about 5.25:1 to about 10:1, orabout 5.5:1 to about 10:1, or about 5.75:1 to about 10:1, or about 6:1to about 10:1, or about 6.25:1 to about 10:1, or about 6.5:1 to about10:1, or about 6.75:1 to about 10:1, or about 7:1 to about 10:1, orabout 7.25:1 to about 10:1, or about 7.5:1 to about 10:1, or about7.75:1 to about 10:1, or about 8:1 to about 10:1, or about 8.25:1 toabout 10:1, or about 8.5:1 to about 10:1, or about 8.75:1 to about 10:1,or about 9:1 to about 10:1.

The polyurea grease compositions of this disclosure afford improvedperformance advantages in structural stability in high temperatureenvironments in the DIN 51821 (FAG FE9) test method. An advantageprovided by this disclosure is the use of a grease in high temperatureenvironments such as steel mills and paper mills that allows for longerlife of the grease in such environments. Also, the grease enhanceslube-for-life applications, where the grease is place in a sealedbearing and the bearing (under its intended application) exceeds thelife of the mechanism it is supporting. This translates to longerequipment run life for the equipment operators between maintenance andthereby cost savings for them. This also improves reliability of thegrease in lubricating the equipment in high temperature conditions forlonger periods of time.

In particular, the grease compositions of this disclosure expand theapplicability of greases in high temperature environments as typicallyfound in paper mills and steel mills and roller bearings. The greasecompositions of this disclosure can also extend the in-service lifethereby reducing the need for intermittent servicing of the equipment(for replacement of the grease) that the grease is being used in, whileproviding adequate lubrication protection to the equipment during theperiod of use. This advantage in turn increases the productivity andlife of the equipment.

An aspect of the present disclosure provides grease compositions withimproved structural stability and resistance to breaking down inaccordance with the DIN 51821 (FAG FE9) test method, relative to othergreases, under extreme conditions, such as high temperatureenvironments.

In any aspect or embodiment described herein, when the greasecompositions of this disclosure are tested using a Mini-Traction Machine(MTM) at 100° C., 1.0 GPa, 50% slide/roll ratio (SRR), and 3.0 m/s-0m/s, coefficient of friction is improved, as compared to coefficient offriction achieved using a grease composition containing other than thepolyurea thickener contained in the grease compositions of thisdisclosure.

The grease compositions of this disclosure can be used in automobiles,diesel engines, axles, transmissions, and industrial applications.Grease compositions must meet the specifications for their intendedapplication as defined by the concerned governing organization. Inparticular, the grease compositions of this disclosure provide optimumperformance in a wide variety of diverse industrial and automotiveapplications. For example: sealed for life applications, electricmotors, automotive wheel bearings, paper machine roll bearings (wet anddry), and wind turbines require different degrees of structuralstability and oil release rates, responding to mechanical and thermalstress.

Advantages of formulating the grease compositions of this disclosurewith prepolymer isocyanates include, for example, the following: (i)prepolymer isocyantes are less than half the price of isocyanatescurrently used to manufacture MDI grease thickeners; prepolymerisocyanates can be made by conventional means; that is, no change isnecessary in the handling or manufacturing of the product; prepolymerisocyanates produce greases that, as compared to conventional MDI basegrease, having superior high temperature properties; and MTM data showsthat combinations of prepolymer isocyanate based thickeners provide alower coefficient of friction that that of current MDI base thickenersystems.

Isocyanate-Terminated Prepolymers

The polyurea thickeners useful in this disclosure are prepared byreacting an isocyanate-terminated prepolymer with at least one amineunder reaction conditions sufficient to prepare the at least onepolyurea thickener.

The isocyanate-terminated prepolymers useful in this disclosure areformed by combining an excess of diisocyanate with polyol.

As shown below, one of the NCO groups of the diisocyanate reacts withone of the OH groups of the polyol; the other end of the polyol reactswith another diisocyanate. The resulting prepolymer has an isocyanategroup on both ends. The prepolymer is a diisocyanate itself, and itreacts like a diisocyanate but with several important differences. Whencompared with the original diisocyanate, the prepolymer has a greatermolecular weight, a higher viscosity, a lower isocyanate content byweight (% NCO), and a lower vapor pressure.

Instead of a diol, a triol or higher functional polyol can also be usedfor the polyol in the reaction, as long as an excess amount ofdiisocyanate is used. Molar ratios of diisocyanate to polyol greaterthan two to one can also be used. These are called quasi-prepolymers.

The isocyanate-terminated prepolymers have an isocyanate content ofabout 0.5 to about 40 weight percent, or about 1.0 to about 35 weightpercent, or about 1.5 to about 30 weight percent, or about 2.0 to about25 weight percent, or about 1.0 to about 20 weight percent, or about 1.5to about 20 weight percent, or about 2.0 to about 20 weight percent, orabout 2.5 to about 20 weight percent, based on the weight of theprepolymer after reaction.

Illustrative isocyanate-terminated prepolymers useful in this disclosureinclude, for example, TDI-ether, TDI-ester, TDI-lactone, MDI-ether,MDI-ester, MDI-lactone, H(12)MDI-ether, H(12)MDI-ester,H(12)MDI-lactone, HDI-ether, HDI-ester, HDI-lactone, IPDI-ether,IPDI-ester, IPDI-lactone, PPDI-ether, PPDI-ester, PPDI-lactone, andmixtures thereof.

In an embodiment, the isocyanate-terminated prepolymers are made fromdiisocyanates selected from 2,4-toluene diisocyanate; 2,6-toluenediisocyanate; 4,4′-diisocyanatodiphenylmethane (MDI); p-phenylenediisocyanate (PPDI); diphenyl-4,4′-diisocyanate;dibenzyl-4,4′-diisocyanate; stilbene-4,4′-diisocyanate;benzophenone-4,4′-diisocyanate; 1,3- and 1,4-xylene diisocyanates; andmixtures thereof.

In another embodiment, the isocyanate-terminated prepolymers are madefrom diisocyanates or polyisocyanates selected from 1,6-hexamethylenediisocyanate (HDI); 1,3-cyclohexyl diisocyanate; 1,4-cyclohexyldiisocyanate (CHDI); saturated diphenylmethane diisocyanate H(12)MDI;bis {4-isocyanatocyclohexyl}methane; 4,4′-methylene dicyclohexyldiisocyanate; 4,4-methylene bis (dicyclohexyl)diisocyanate; methylenedicyclohexyl diisocyanate; methylene bis (4-cyclohexylene isocyanate);saturated methylene diphenyl diisocyanate; saturated methyl diphenyldiisocyanate); isophorone diisocyanate (IPDI); hexamethylenediisocyanate (HDI); 2,2,4-trimethyl-1,6-hexamethylene diisocyanate2,4,4-trimethyl-1,6-hexamethylene diisocyanate; dodecamethylenediisocyanate; 1,4-diisocyanatocyclohexane;1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane (IPDI); 2,4′-and/or 4,4′-diisocyanato-dicyclohexyl methane; 2,4-diisocyanato-diphenylmethane; 4,4′-diisocyanato-diphenyl methane; 2,4-diisocyanatotoluene;2,6-diisocyanatotoluene; and mixtures of these isomers with their higherhomologues.

In a further embodiment, the isocyanate-terminated prepolymers are madefrom diisocyanates or polyisocyanates selected from hexamethylenediisocyanate (HDI); 2,2,4-trimethyl-1,6-hexamethylene diisocyanates;2,4,4-trimethyl-1,6-hexamethylene diisocyanate; dodecamethylenediisocyanate; 1,4-diisocyanatocyclohexane;1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane;2,4′-diisocyanato-dicyclohexyl methane; 4,4′-diisocyanato-dicyclohexylmethane; 2,4-diisocyanato-diphenyl methane; 4,4′-diisocyanato-diphenyl2,4-diisocyanatotoluene; 2,6-diisocyanatotoluene; and any mixtures ofthese compounds and their higher homologues.

In an embodiment, the isocyanate-terminated prepolymers are a reactionproduct of a diisocyanate or polyisocyanate with a polyol selected frompolyester polyols, polycaprolactone polyols, and polyether polyols.

In another embodiment, the isocyanate-terminated prepolymers are areaction product of a diisocyanate or polyisocyanate with a polyolselected from polyester polyols, polycaprolactone polyols, polyetherpolyols, polyhydroxy polycarbonates, polyhydroxy polyacetals,polyhydroxy polyacrylates, polyhydroxy polyester amides and polyhydroxypolythioethers or mixtures thereof. The polyols have at least twohydroxyl groups per molecule and have a hydroxyl group content of about0.5 to 20 weight percent.

In an embodiment, the isocyanate-terminated prepolymers are a reactionproduct of a diisocyanate or polyisocyanate with one or more polyolsselected from polyester polyols, polycaprolactone polyols, polyetherpolyols, polytetramethylene ether glycol, polyhydroxy polycarbonates,polyhydroxy polyacetals, polyhydroxy polyacrylates, polyhydroxypolyester amides and polyhydroxy polythioethers, or mixtures thereof.

In another embodiment, the isocyanate-terminated prepolymers are thereaction product of a diisocyanate or polyisocyanate selected fromhexamethylene diisocyanate (HDI) and1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane (IPDI), withone or more polyols selected from one or more polyether polyols andpolyester polyols.

In a further embodiment, the isocyanate-terminated prepolymers are thereaction product of a diisocyanate or polyisocyanate selected fromhexamethylene diisocyanate (HDI) and1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane (IPDI) withone or more polyols selected from polyether polyols or polycaprolactonepolyols.

The isocyanates useful in this disclosure can be aromatic or aliphatic.Useful aromatic diisocyanates can include, for example, 2,4-toluenediisocyanate and 2,6-toluene diisocyanate (each generally referred to asTDI); mixtures of the two TDI isomers; 4,4′-diisocyanatodiphenylmethane(MDI); p-phenylene diisocyanate (PPDI); diphenyl-4,4′-diisocyanate;dibenzyl-4,4′-diisocyanate; stilbene-4,4′-diisocyanate;benzophenone-4,4′-diisocyanate; 1,3- and 1,4-xylene diisocyanates; orthe like, or a combination comprising at least one of the foregoingaromatic isocyanates. Exemplary aromatic diisocyanates for thepreparation of polyurethane prepolymers include TDI, MDI, and PPDI.

Useful aliphatic diisocyanates can include, for example,1,6-hexamethylene diisocyanate (HDI); 1,3-cyclohexyl diisocyanate;1,4-cyclohexyl diisocyanate (CHDI); saturated diphenylmethanediisocyanate known as H(12)MDI; (also known commercially asbis{4-isocyanatocyclohexyl}methane, 4,4′-methylene dicyclohexyldiisocyanate, 4,4-methylene bis(dicyclohexyl)diisocyanate, methylenedicyclohexyl diisocyanate, methylene bis(4-cyclohexylene isocyanate),saturated methylene diphenyl diisocyanate, and saturated methyl diphenyldiisocyanate); isophorone diisocyanate (IPDI); or the like; or acombination comprising at least one of the foregoing isocyanates. Anexemplary aliphatic diisocyanate is H(12)MDI.

Other exemplary polyisocyanates include hexamethylene diisocyanate(HDI), 2,2,4- and/or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate,dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4′-and/or 4,4′-diisocyanato-dicyclohexyl methane, 2,4- and/or4,4′-diisocyanato-diphenyl methane, and mixtures of these isomers withtheir higher homologues which are obtained by the phosgenation ofaniline/formaldehyde condensates, 2,4- and/or 2,6-diisocyanatotolueneand any mixtures of these compounds.

Illustrative isocyanates useful in preparing the isocyanate-terminatedprepolymers of this disclosure include those of the general formula:

R(NCO)i

wherein R is an organic radical having the valence of i, wherein i isgreater than or equal to about 2. R can be a substituted orunsubstituted hydrocarbon group (e.g., a methylene group or an arylenegroup).

The isocyanate-terminated prepolymers and semi-prepolymers may suitablybe prepared from low molecular weight polyol compounds having amolecular weight of 60 to 300. The polyols can also have a molecularweight of about 300 to about 20,000, preferably about 500 to about10,000, more preferably about 1000 to 5000, as determined from thefunctionality and the OH number. In one embodiment, the polyols can haveat least two hydroxyl groups per molecule and generally have a hydroxylgroup content of about 0.5 to 20 wt %, preferably about 1 to 5 wt %.

Examples of suitable polyols are polyester polyols, polycaprolactonepolyols, polyether polyols, polyhydroxy polycarbonates, polyhydroxypolyacetals, polyhydroxy polyacrylates, polyhydroxy polyester amides andpolyhydroxy polythioethers. Exemplary polyols are polyester polyols,polyether polyols, polyesters derived from lactones (e.g.,8-caprolactone or ω-hydroxycaproic acid), or a combination comprising atleast one of the foregoing polyols.

Suitable polyester polyols include reaction products of polyhydric ordihydric alcohols with polybasic or preferably dibasic carboxylic acids.Instead of these polycarboxylic acids, the corresponding carboxylic acidanhydrides or polycarboxylic acid esters of lower alcohols or mixturesthereof may be used for preparing the polyester polyols. Thepolycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/orheterocyclic and they may be substituted (e.g., by halogen atoms),and/or unsaturated. Examples include succinic acid, adipic acid, subericacid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid,terephthalic acid, trimellitic acid, phthalic acid anhydride,tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride,tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalicacid anhydride, glutaric acid anhydride, maleic acid, maleic acidanhydride, fumaric acid, dimeric and trimeric fatty acids such as oleicacid, which may be mixed with monomeric fatty acids, dimethylterephthalates, bis-glycol terephthalate, or the like, or a combinationcomprising at least one of the foregoing. Polyesters of lactones, e.g.ε-caprolactone or hydroxy-carboxylic acids, e.g. ω-hydroxycaproic acid,may also be used.

The polyether polyols are obtained by the chemical addition of alkyleneoxides, such as, for example, ethylene oxide, propylene oxide andmixtures thereof, to water or polyhydric alcohols, such as, for example,ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butyleneglycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentylglycol, cyclohexane dimethanol (1,4-bis-hydroxymethylcyclohexane),2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, triethyleneglycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol,polypropylene glycol, polytetramethylene glycol, dibutylene glycol andpolybutylene glycol, glycerine, trimethylolpropane, or the like, or acombination comprising at least one of the foregoing polyhydricalcohols.

Examples of suitable starting molecules for the polyether polyolsinclude monomeric polyols, water, organic polyamines having at least twoNH bonds and mixtures of these starting molecules. Ethylene oxide and/orpropylene oxide are particularly suitable alkylene oxides for thealkoxylation reaction. These alkylene oxides may be introduced into thealkoxylation reaction in any sequence or as a mixture.

Suitable polyhydroxy polycarbonates include those obtained by reactingdiols, such as, for example, 1,3-propanediol, 1,4-butanediol and/or1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethyleneglycol with diarylcarbonates or cyclic carbonates. The reaction betweenthe diols and the diarylcarbonates or the cyclic carbonates takes placein the presence of phosgene. Also suitable are polyester carbonatesobtained by reacting the previously described polyesters or polylactoneswith phosgene, diaryl carbonates or cyclic carbonates.

The prepolymers generally have an isocyanate content of about 0.5 toabout 40 weight percent (wt %), based on the weight of the prepolymerafter reaction. In one embodiment, the prepolymers generally have anisocyanate content of about 1 to about 20 wt %, based on the weight ofthe prepolymer after reaction. The prepolymer is generally manufacturedusing starting materials at an NCO/OH equivalent ratio of about 1.05:1to about 10:1, preferably about 1.1:1 to about 3:1. The reaction isoptionally followed by the distillative removal of any unreactedvolatile starting polyisocyanates still present.

Exemplary isocyanate prepolymers are TDI-ether, TDI-ester, TDI-lactone,MDI-ether, MDI-ester, H12MDI-ether, H12MDI-ester and similar prepolymersmade from HDI, IPDI and PPDI. The isocyanate prepolymers with low freeisocyanate monomers are preferred. Although preferredisocyanate-terminated prepolymers are based on TDI and H12MDI, otherprepolymers can be used to formulate the polyurea thickener.

Examples of suitable commercially available prepolymers are LUPRANATE®5030, LUPRANATE® MP-102, and LUPRANATE® 5070 prepolymers, all of whichare commercially available from BASF. Each of these three prepolymers(i.e., composition of the commercial product) have a slight excess of4-4′ and 2-4′ MDI as described by BASF.

Reaction conditions for the reaction of the polyisocyanate with apolyol, such as temperature, pressure and contact time, may vary greatlyand any suitable combination of such conditions may be employed herein.The reaction temperature may be between about 10° C. to about 150° C.,and most preferably between about 20° C. to about 80° C. Normally thereaction is carried out under ambient pressure and the contact time mayvary from a matter of seconds or minutes to a few hours or greater. Thereactants can be added to the reaction mixture or combined in any order.The stir time employed can range from about 0.1 to about 400 hours,preferably from about 1 to 75 hours, and more preferably from about 1 to16 hours. The prepolymer is prepared by reacting starting materials atan NCO/OH equivalent ratio of about 1.05:1 to about 10:1.

It has been surprisingly found that viable grease thickener was madewith the prepolymer isocyanates using traditional amine components andgrease manufacturing assets. There is a performance benefit in thegreases made with the prepolymer isocyanates, in particular, theyexhibit product stability, desirable high temperature performance andinherent low noise characteristics. Products formulated with theisocyanate prepolymer, or combinations thereof, are very stable. Withrespect to thickener products formulated with the isocyanate prepolymer,or combinations thereof, the finished thickener products are inherentlylow noise. With respect to products formulated with the isocyanateprepolymer, or combinations thereof, the finished grease products havecomparatively better high temperature performance than conventionalpolyurea grease products. With respect to products formulated with theisocyanate prepolymer, or combinations thereof, the finished greaseproducts exhibit lower coefficient of friction as presented in Stribeckanalysis.

Polyurea Thickeners

The polyurea thickeners useful in this disclosure are prepared byreacting an isocyanate-terminated prepolymer with at least one amineunder reaction conditions sufficient to prepare the polyurea thickener.

Illustrative isocyanate-terminated prepolymers include, for example,TDI-ether, TDI-ester, TDI-lactone, MDI-ether, MDI-ester, H12MDI-ether,H12MDI-ester and similar prepolymers made from HDI, IPDI and PPDI. Theisocyanate prepolymers with low free isocyanate monomers are preferred.Although preferred isocyanate-terminated prepolymers are based on TDIand H12MDI, other prepolymers can be used to formulate the polyureathickeners.

Illustrative amines useful in this disclosure include aromatic,alicyclic and aliphatic amines. The monoamines reacted with theisocyanate-terminated prepolymers will form terminal hydrocarbon endgroups on the polyurea thickener. The diamines reacted with theisocyanate-terminated prepolymers will form terminal amine end groups onthe polyurea thickener for further reaction with otherisocyanate-terminated prepolymers. These terminal end groups will havefrom 1 to 30 carbon atoms, but are preferably from 5 to 28 carbon atoms,and more desirably from 10 to 24 carbon atoms.

Illustrative of various monoamines are pentylamine, hexylamine,heptylamine, octylamine, decylamine, dodecylamine, tetradecylamine,hexadecylamine, octadecylamine, eicosylamine, dodecenylamine,hexadecenylamine, octadecenylamine, octadecadienylamine, abietylamine,aniline, toluidine, naphthylamine, cumylamine, bomylamine, fenchylamine,tertiary butyl aniline, benzylamine, β-phenethylamine, etc. Otherillustrative amines are prepared from natural fats and oils or fattyacids obtained therefrom. These materials can be reacted with ammonia togive first amides and then nitriles. The nitriles are then reduced toamines, conveniently by catalytic hydrogenation. Exemplary aminesprepared by the method include stearylamine, laurylamine, palmitylamine,oleylamine, petroselinylamine, linoleylamine, linolenylamine,eleostearylamine, and the like. The unsaturated amines are particularlypreferred.

Illustrative of various diamines are ethylenediamine, propanediamine,butanediamine, hexanediamine, dodecanediamine, octanediamine,hexadecanediamine, cyclohexanediamine, cyclooctanediamine,phenylenediamine, tolylenediamine, xylylenediamine, dianiline methane,ditoluidinemethane, bis(aniline), bis(toluidine) and piperazine, and thelike.

In an embodiment, the greases of this disclosure having a polyureathickener exhibit improved structural stability and resistance tobreaking down and losing their consistency under the effect of hightemperature conditions.

The grease compositions of this disclosure may include the polyureathickener in a range from about 0.5 to about 20 wt. % (e.g., about 0.5to about 10 wt. %). For example, the grease composition of the presentdisclosure may have polyurea thickener present in an amount of about 0.5wt. % to about 20 wt. %, about 0.5 wt. % to about 17.5 wt. %, about 0.5wt. % to about 15 wt. %, about 0.5 wt. % to about 12.5 wt. %, about 0.5wt. % to about 10 wt. %, about 0.5 wt. % to about 7.5 wt. %, about 0.5wt. % to about 5 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. %to about 17.5 wt. %, about 1 wt. % to about 15 wt. %, about 1 wt. % toabout 12.5 wt. %, about 1 wt. % to about 10 wt. %, about 1 wt. % toabout 7.5 wt. %, about 1 wt. % to about 5 wt. %, about 2.5 wt. % toabout 20 wt. %, about 2.5 wt. % to about 17.5 wt. %, about 2.5 wt. % toabout 15 wt. %, about 2.5 wt. % to about 12.5 wt. %, about 2.5 wt. % toabout 10 wt. %, about 2.5 wt. % to about 7.5 wt. %, about 5 wt. % toabout 20 wt. %, about 5 wt. % to about 17.5 wt. %, about 5 wt. % toabout 15 wt. %, about 5 wt. % to about 12.5 wt. %, about 5 wt. % toabout 10 wt. %, about 7.5 wt. % to about 20 wt. %, about 7.5 wt. % toabout 17.5 wt. %, about 7.5 wt. % to about 15 wt. %, about 7.5 wt. % toabout 12.5 wt. %, about 10 wt. % to about 20 wt. %, about 10 wt. % toabout 17.5 wt. %, about 10 wt. % to about 15 wt. %, about 12.5 wt. % toabout 20 wt. %, about 12.5 wt. % to about 17.5 wt. %, or about 15 wt. %to about 20 wt. %.

Reaction conditions for the reaction of the isocyanate-terminatedprepolymer with at least one amine, such as temperature, pressure andcontact time, may vary greatly and any suitable combination of suchconditions may be employed herein. The reaction temperature may bebetween about 10° C. to about 150° C., and most preferably between about20° C. to about 80° C. Normally the reaction is carried out underambient pressure and the contact time may vary from a matter of secondsor minutes to a few hours or greater. The reactants can be added to thereaction mixture or combined in any order. The stir time employed canrange from about 0.1 to about 400 hours, preferably from about 1 to 75hours, and more preferably from about 1 to 16 hours.

Polyurea thickeners are compounds containing the urea group (—NHCONH—)in their molecular structure. These compounds include mono-, di-, tri-,tetra- and polyurea compounds, depending upon the number of urealinkages they contain. Polyurea is the preferred thickener for use inthe compositions of this disclosure.

A grease composition according to this disclosure may contain more thanone polyurea thickener.

Lubricating Base Oils

In any aspect or embodiment described herein, the lubricating base oilor oils comprise at least one of: a Group I oil, a Group II oil (e.g.,at least one of Group II light neutral oil such as a Group II oil with aKV100 of about 4-6 cSt, Group II heavy neutral oil such as a Group IIoil with a KV100 of ≥11 cST, or a combination thereof), a Group III oil,a Group IV oil, a Group V oil, a gas-to-liquid oil, a polyalphaolefin,or combinations thereof. For example, the lubricating base oil or oilsinclude at least one Group I oil, Group II oil, mineral oil, or acombination thereof. Lubricating oil may be present in the compositionof present disclosure in an amount of about 50 to about 90 wt. % (e.g.from about 70 to about 85 wt. %) of the grease composition. For example,the grease composition of the present disclosure may include about 50wt. % to about 90 wt. %, about 50 wt. % to about 85 wt. %, about 50 wt.% to about 80 wt. %, about 50 wt. % to about 75 wt. %, about 50 wt. % toabout 70 wt. %, about 50 wt. % to about 65 wt. %, about 50 wt. % toabout 60 wt. %, about 55 wt. % to about 90 wt. %, about 55 wt. % toabout 85 wt. %, about 55 wt. % to about 80 wt. %, about 55 wt. % toabout 75 wt. %, about 55 wt. % to about 70 wt. %, about 55 wt. % toabout 65 wt. %, about 60 wt. % to about 90 wt. %, about 60 wt. % toabout 85 wt. %, about 60 wt. % to about 80 wt. %, about 60 wt. % toabout 75 wt. %, about 60 wt. % to about 70 wt. %, about 65 wt. % toabout 90 wt. %, about 65 wt. % to about 85 wt. %, about 65 wt. % toabout 80 wt. %, about 65 wt. % to about 75 wt. %, about 70 wt. % toabout 90 wt. %, about 70 wt. % to about 85 wt. %, about 70 wt. % toabout 80 wt. %, about 75 wt. % to about 90 wt. %, about 75 wt. % toabout 85 wt. %, or about 80 wt. % to about 90 wt. %.

Groups I, II, III, IV and V are broad base oil stock categories, thecharacteristics of which are summarized in Table 1 below, developed anddefined by the American Petroleum Institute (API Publication 1509;www.API.org) to create guidelines for lubricant base oils. Group I basestocks have a viscosity index of between about 80 to about 120 andcontain greater than about 0.03% sulfur and/or less than about 90%saturates. Group II base stocks have a viscosity index of between about80 to about 120, and contain less than or equal to about 0.03% sulfurand greater than or equal to about 90% saturates. Group III stocks havea viscosity index greater than about 120 and contain less than or equalto about 0.03% sulfur and greater than about 90% saturates. Group IVincludes polyalphaolefins (PAO). Group V base stock includes base stocksnot included in Groups I-IV.

TABLE 1 Properties of Base Oil Groups Base Oil Properties SaturatesSulfur Viscosity Index Group I <90 and/or >0.03% and >80 and <120 GroupII ≥90 and ≤0.03% and ≥80 and <120 Group III ≥90 and ≤0.03% and ≥120Group IV polyalphaolefins (PAO) Group V All other base oil stocks notincluded in Groups I, II, III or IV

Natural oils include animal oils, vegetable oils (castor oil and lardoil, for example), and mineral oils. Animal and vegetable oilspossessing favorable thermal oxidative stability can be used. Of thenatural oils, mineral oils are preferred. Mineral oils vary widely as totheir crude source, for example, as to whether they are paraffinic,naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal orshale are also useful. Natural oils vary also as to the method used fortheir production and purification, for example, their distillation rangeand whether they are straight run or cracked, hydrorefined, or solventextracted.

Group II and/or Group III hydroprocessed or hydrocracked base stocks arealso well known base stock oils.

Synthetic oils include hydrocarbon oil. Hydrocarbon oils include oilssuch as polymerized and interpolymerized olefins (polybutylenes,polypropylenes, propylene isobutylene copolymers, ethylene-olefincopolymers, and ethylene-alphaolefin copolymers, for example).Polyalphaolefin (PAO) oil base stocks are commonly used synthetichydrocarbon oil. By way of example, PAOs derived from C₈, C₁₀, C₁₂, C₁₄olefins or mixtures thereof may be utilized. See U.S. Pat. Nos.4,956,122; 4,827,064; and 4,827,073.

The average molecular weights of the PAOs, which are known materials andgenerally available on a major commercial scale from suppliers such asExxonMobil Chemical Company, Chevron Phillips Chemical Company, BP, andothers, can vary from about 250 to about 3,000, although PAO's may bemade in viscosities up to about 150 cSt (100° C.). The PAOs aretypically comprised of relatively low molecular weight hydrogenatedpolymers or oligomers of alphaolefins which include, but are not limitedto, C₂ to about C₃₂ alphaolefins with the C₈ to about C₁₆ alphaolefins,such as 1-octene, 1-decene, 1-dodecene and the like. For example, thepolyalphaolefins can be poly-1-octene, poly-1-decene, poly-1-dodecene, acombination thereof, or mixed olefin-derived polyolefins. However, thedimers of higher olefins in the range of C₁₂ to C₁₈ may be used toprovide low viscosity base stocks of acceptably low volatility.Depending on the viscosity grade and the starting oligomer, the PAOs maybe predominantly dimers, trimers and tetramers of the starting olefins,with minor amounts of the lower and/or higher oligomers, having aviscosity range of 1.5 cSt to 12 cSt. PAO fluids of particular use mayinclude 3 cSt, 3.4 cSt, and/or 3.6 cSt and combinations thereof.Mixtures of PAO fluids having a viscosity range of 1.5 cSt toapproximately 150 cSt or more may be used if desired. Unless indicatedotherwise, all viscosities cited herein are measured at 100° C.

The PAO fluids may be conveniently made by the polymerization of analphaolefin in the presence of a polymerization catalyst such as theFriedel-Crafts catalysts including, for example, aluminum trichloride,boron trifluoride or complexes of boron trifluoride with water, alcoholssuch as ethanol, propanol or butanol, carboxylic acids or esters such asethyl acetate or ethyl propionate. For example the methods disclosed byU.S. Pat. No. 4,149,178 or 3,382,291 may be conveniently used herein.Other descriptions of PAO synthesis are found in the following U.S. Pat.Nos. 3,742,082; 3,769,363; 3,876,720; 4,239,930; 4,367,352; 4,413,156;4,434,408; 4,910,355; 4,956,122; and 5,068,487. The dimers of the C₁₄ toC₁₈ olefins are described in U.S. Pat. No. 4,218,330.

Other useful lubricant oil base stocks include wax isomerate base stocksand base oils, comprising hydroisomerized waxy stocks (e.g. waxy stockssuch as gas oils, slack waxes, fuels hydrocracker bottoms, etc.),hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids (GTL) base stocksand base oils, and other wax isomerate hydroisomerized base stocks andbase oils, or mixtures thereof. Fischer-Tropsch waxes, the high boilingpoint residues of Fischer-Tropsch synthesis, are highly paraffinichydrocarbons with very low sulfur content. The hydroprocessing used forthe production of such base stocks may use an amorphoushydrocracking/hydroisomerization catalyst, such as one of thespecialized lube hydrocracking (LHDC) catalysts or a crystallinehydrocracking/hydroisomerization catalyst, such as a zeolitic catalyst.For example, one useful catalyst is ZSM-48 as described in U.S. Pat. No.5,075,269, the disclosure of which is incorporated herein by referencein its entirety. Processes for making hydrocracked/hydroisomerizeddistillates and hydrocracked/hydroisomerized waxes are described, forexample, in U.S. Pat. Nos. 2,817,693; 4,975,177; 4,921,594 and 4,897,178as well as in British Patent Nos. 1,429,494; 1,350,257; 1,440,230 and1,390,359. Each of the aforementioned patents is incorporated herein intheir entirety. Particularly favorable processes are described inEuropean Patent Application Nos. 464546 and 464547, also incorporatedherein by reference. Processes using Fischer-Tropsch wax feeds aredescribed in U.S. Pat. Nos. 4,594,172 and 4,943,672, the disclosures ofwhich are incorporated herein by reference in their entirety.

Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils,and other wax-derived hydroisomerized (wax isomerate) base oils may beused in the present disclosure, and may have kinematic viscosities at100° C. of about 2 cSt to about 50 cSt, e.g. about 2 cSt to about 30 cStor about 3 cSt to about 25 cSt, as exemplified by GTL 4 with kinematicviscosity of about 4.0 cSt at 100° C. and a viscosity index of about141. These Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derivedbase oils, and other wax-derived hydroisomerized base oils may haveuseful pour points of about −20° C. or lower, and under some conditionsmay have advantageous pour points of about −25° C. or lower, with usefulpour points of about −30° C. to about −40° C. or lower. Usefulcompositions of Gas-to-Liquids (GTL) base oils, Fischer-Tropsch waxderived base oils, and wax-derived hydroisomerized base oils are recitedin U.S. Pat. Nos. 6,080,301; 6,090,989, and 6,165,949 for example, andare incorporated herein in their entirety by reference.

The hydrocarbyl aromatics can be used as a base oil or base oilcomponent and can be any hydrocarbyl molecule in which at least about 5%of its weight is derived from an aromatic moiety, such as a benzenoidmoiety or naphthenoid moiety, or their derivatives. These hydrocarbylaromatics include alkyl benzenes, alkyl naphthalenes, alkyl biphenyls,alkyl diphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides,alkylated bis-phenol A, alkylated thiodiphenol, and the like. Thearomatic can be mono-alkylated, dialkylated, polyalkylated, and thelike. The aromatic can be mono-functionalized or poly-functionalized.The hydrocarbyl groups can also be comprised of mixtures of alkylgroups, alkenyl groups, alkynyl, cycloalkyl groups, cycloalkenyl groupsand other related hydrocarbyl groups. The hydrocarbyl groups can rangefrom about C₆ up to about C₆₀ with a range of about C₈ to about C₂₀often being preferred. A mixture of hydrocarbyl groups may be utilized,and up to about three such substituents may be present. The hydrocarbylgroup can optionally contain sulfur, oxygen, and/or nitrogen containingsubstituents. The aromatic group can also be derived from natural(petroleum) sources, provided at least about 5% of the molecule iscomprised of an above-type aromatic moiety. In certain embodiments, theviscosity at 100° C. is approximately 2 cSt to about 50 cSt, e.g.approximately 3 cSt to about 20 cSt for the hydrocarbyl aromaticcomponent. In one embodiment, an alkyl naphthalene where the alkyl groupis primarily comprised of 1-hexadecene is used. Other alkylates ofaromatics can be advantageously used. Naphthalene or methyl naphthalene,for example, can be alkylated with olefins such as octene, decene,dodecene, tetradecene or higher, mixtures of similar olefins, and thelike. Alkylated naphthalene and analogues may also comprise compositionswith isomeric distribution of alkylating groups on the alpha and betacarbon positions of the ring structure. Distribution of groups on thealpha and beta positions of a naphthalene ring may range from 100:1 to1:100, more often 50:1 to 1:50 Useful concentrations of hydrocarbylaromatic in a lubricant oil composition can be about 2% to about 25%,e.g. about 4% to about 20% or about 4% to about 15%, depending on theapplication.

Alkylated aromatics such as the hydrocarbyl aromatics of the presentdisclosure may be produced by well-known Friedel-Crafts alkylation ofaromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G.A. (ed.), Inter-science Publishers, New York, 1963. For example, anaromatic compound, such as benzene or naphthalene, is alkylated by anolefin, alkyl halide or alcohol in the presence of a Friedel-Craftscatalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1,chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-sciencePublishers, New York, 1964. Many homogeneous or heterogeneous, solidcatalysts are known to one skilled in the art. The choice of catalystdepends on the reactivity of the starting materials and product qualityrequirements. For example, strong acids such as AlCl₃, BF₃, or HF may beused. In some cases, milder catalysts such as FeCl₃ or SnCl₄ arepreferred. Newer alkylation technology uses zeolites or solid superacids.

Esters comprise a useful base stock. Additive solvency and sealcompatibility characteristics may be secured by the use of esters suchas the esters of dibasic acids with monoalkanols and the polyol estersof monocarboxylic acids. Esters of the former type include, for example,the esters of dicarboxylic acids such as phthalic acid, succinic acid,alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid,suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.,with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, etc. Specific examples of these types ofesters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexylfumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate,dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, etc.

Useful synthetic esters are those which are obtained by reacting one ormore polyhydric alcohols, such as hindered polyols (including theneopentyl polyols, e.g., neopentyl glycol, trimethylol ethane,2-methyl-2-propyl-1,3-propanediol, trimethylol propane, pentaerythritoland dipentaerythritol) with alkanoic acids containing at least about 4carbon atoms, e.g. C₅ to C₃₀ acids such as saturated straight chainfatty acids including caprylic acid, capric acid, lauric acid, myristicacid, palmitic acid, stearic acid, arachic acid, and behenic acid, orthe corresponding branched chain fatty acids or unsaturated fatty acidssuch as oleic acid, or mixtures of any of these materials.

Suitable synthetic ester components include the esters of trimethylolpropane, trimethylol butane, trimethylol ethane, pentaerythritol and/ordipentaerythritol with one or more monocarboxylic acids containing fromabout 5 to about 10 carbon atoms. These esters are widely availablecommercially, for example, the Mobil P-41 and P-51 esters of ExxonMobilChemical Company (Irving, Tex., USA).

Also useful are esters derived from renewable material, such as coconut,palm, rapeseed, soy, sunflower and the like. These esters may bemonoesters, di-esters, polyol esters, complex esters, or mixturesthereof. These esters are widely available commercially, for example,the Esterex NP 343 of ExxonMobil Chemical Company (Irving, Tex., USA).For example, the renewable content of the ester may be greater thanabout 70 weight percent, such as more than about 80 weight percent ormore than about 90 weight percent.

Other useful fluids of lubricating viscosity include non-conventional orunconventional base stocks that have been processed, e.g. catalytically,or synthesized to provide high performance lubrication characteristics.

Non-conventional or unconventional base stocks/base oils include one ormore of a mixture of base stock(s) derived from one or moreGas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate basestock(s) derived from natural wax or waxy feeds, mineral and ornon-mineral oil waxy feed stocks such as slack waxes, natural waxes, andwaxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxyraffinate, hydrocrackate, thermal crackates, or other mineral, mineraloil, or even non-petroleum oil derived waxy materials such as waxymaterials received from coal liquefaction or shale oil, and mixtures ofsuch base stocks.

GTL materials are materials that are derived via one or more synthesis,combination, transformation, rearrangement, and/ordegradation/deconstructive processes from gaseous carbon-containingcompounds, hydrogen-containing compounds and/or elements as feed stockssuch as hydrogen, carbon dioxide, carbon monoxide, water, methane,ethane, ethylene, acetylene, propane, propylene, propyne, butane,butylenes, and butynes. GTL base stocks and/or base oils are GTLmaterials of lubricating viscosity that are generally derived fromhydrocarbons; for example, waxy synthesized hydrocarbons, that arethemselves derived from simpler gaseous carbon-containing compounds,hydrogen-containing compounds and/or elements as feed stocks. GTL basestock(s) and/or base oil(s) include oils boiling in the lube oil boilingrange (1) separated/fractionated from synthesized GTL materials such as,for example, by distillation and subsequently subjected to a final waxprocessing step which involves either or both of a catalytic dewaxingprocess, or a solvent dewaxing process, to produce lube oils ofreduced/low pour point; (2) synthesized wax isomerates, comprising, forexample, hydrodewaxed or hydroisomerized cat and/or solvent dewaxedsynthesized wax or waxy hydrocarbons; (3) hydrodewaxed orhydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T)material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possibleanalogous oxygenates); such as hydrodewaxed or hydroisomerized/followedby cat and/or solvent dewaxing dewaxed F-T waxy hydrocarbons, orhydrodewaxed or hydroisomerized/followed by cat (or solvent) dewaxingdewaxed, F-T waxes, or mixtures thereof.

GTL base stock(s) and/or base oil(s) derived from GTL materials,especially, hydrodewaxed or hydroisomerized/followed by cat and/orsolvent dewaxed wax or waxy feed, preferably F-T material derived basestock(s) and/or base oil(s), are characterized typically as havingkinematic viscosities at 100° C. of from about 2 mm²/s to about 50 mm²/s(ASTM D445). They are further characterized typically as having pourpoints of −5° C. to about −40° C. or lower (ASTM D97). They are alsocharacterized typically as having viscosity indices of about 80 to about140 or greater (ASTM D2270).

In addition, the GTL base stock(s) and/or base oil(s) are typicallyhighly paraffinic (>90% saturates), and may contain mixtures ofmonocycloparaffins and multicycloparaffins in combination withnon-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stock(s) and/or base oil(s)typically have very low sulfur and nitrogen content, generallycontaining less than about 10 ppm, and more typically less than about 5ppm of each of these elements. The sulfur and nitrogen content of GTLbase stock(s) and/or base oil(s) obtained from F-T material, especiallyF-T wax, is essentially nil. In addition, the absence of phosphorus andaromatics make this materially especially suitable for the formulationof low SAP products.

The term GTL base stock and/or base oil and/or wax isomerate base stockand/or base oil is to be understood as embracing individual fractions ofsuch materials of wide viscosity range as recovered in the productionprocess, mixtures of two or more of such fractions, as well as mixturesof one or two or more low viscosity fractions with one, two or morehigher viscosity fractions to produce a blend wherein the blend exhibitsa target kinematic viscosity.

The GTL material, from which the GTL base stock(s) and/or base oil(s)is/are derived is preferably an F-T material (i.e., hydrocarbons, waxyhydrocarbons, wax).

The grease composition of the present disclosure may use any of thevariety of oils corresponding to API Group I, Group II, Group III, GroupIV, and Group V oils and mixtures thereof, e.g. API Group I oil, APIGroup II oil, mineral oil, or a combination thereof, may be utilized inthe compositions of the present disclosure.

Performance Additives

The composition of the present disclosure may include small amounts ofat least one (e.g., 1, 2, 3, 4, 5, or 6, or more) performance additive.For example, the composition of the present disclosure may include atleast one of anticorrosive agent or corrosion inhibitor, an extremepressure additive, an antiwear agent, a pour point depressants, anantioxidant or oxidation inhibitor, a rust inhibitor, a metaldeactivator, a dispersant, a demulsifier, a dye or colorant/chromophoricagent, a seal compatibility agent, a friction modifier, a viscositymodifier/improver, a viscosity index improver, or combinations thereof.For example, solid lubricants such as molybdenum disulfide and graphitemay be present in the composition of the present disclosure, such asfrom about 1 to about 5 wt. % (e.g., from about 1.5 to about 3 wt. %)for molybdenum disulfide and from about 3 to about 15. wt. % (e.g., fromabout 6 to about 12 wt. %) for graphite.

The amounts of individual additives will vary according to the additiveand the level of functionality to be provided by it.

The presence or absence of these lubricating oil performance additivesdoes not adversely affect the compositions of the present disclosure.For a review of many commonly used additives, see Klamann in Lubricantsand Related Products, Verlag Chemie, Deerfield Beach, Fla.; ISBN 0 89573177 0. Reference is also made to “Lubricant Additives” by M. W. Ranney,published by Noyes Data Corporation of Parkridge, N.J. (1973) and“Lubricant Additives: Chemistry and Applications” edited by L. R.Rudnick, published by CRC Press of Boca Raton, Fla. (2009). Theperformance additives useful in the present disclosure do not have to besoluble in the lubricating oils. Insoluble additives in oil can bedispersed in the lubricating oils of the present disclosure. The typesand quantities of performance additives used in combination with thecompositions of the present disclosure are not limited by the examplesshown herein as illustrations.

As such, in any aspect or embodiment described herein, the compositionfurther comprises at least one of anticorrosive agent or corrosioninhibitor, an extreme pressure additive, an antiwear agent, a pour pointdepressants, an antioxidant or oxidation inhibitor, a rust inhibitor, ametal deactivator, a dispersant, a demulsifier, a dye orcolorant/chromophoric agent, a seal compatibility agent, a frictionmodifier, a viscosity modifier/improver, a viscosity index improver, orcombinations thereof. In any aspect or embodiment described herein, thedispersant includes succinimide-type dispersant. Unless specifiedotherwise, the performance additive or performance additives listedabove are present in a total amount equal to or less than about 10 wt.%, equal to or less than about 9.5 wt. %, equal to or less than about 9wt. %, equal to or less than about 8.5 wt. %, equal to or less thanabout 8 wt. %, equal to or less than about 7.5 wt. %, equal to or lessthan about 7 wt. %, equal to or less than about 6.5 wt. %, equal to orless than about 6 wt. %, equal to or less than about 5.5 wt. %, equal toor less than about 5 wt. %, equal to or less than about 4.5 wt. %, equalto or less than about 4 wt. %, equal to or less than about 3.5 wt. %,equal to or less than about 3 wt. %, equal to or less than about 2.5 wt.%, equal to or less than about 2 wt. %, equal to or less than about 1.5wt. %, or equal to or less than about 0.5 wt. %. For example, theperformance additive or performance additives are present in a totalamount of about 0.1 to about 10 wt. %, about 0.1 to about 9 wt. %, about0.1 to about 8 wt. %, about 0.1 to about 7 wt. %, about 0.1 to about 6wt. %, about 0.1 to about 5 wt. %, about 0.1 to about 4 wt. %, about 0.1to about 3 wt. %, about 0.1 to about 2 wt. %, about 0.1 to about 1 wt.%, about 0.5 to about 10 wt. %, about 0.5 to about 9 wt. %, about 0.5 toabout 8 wt. %, about 0.5 to about 7 wt. %, about 0.5 to about 6 wt. %,about 0.5 to about 5 wt. %, about 0.5 to about 4 wt. %, about 0.5 toabout 3 wt. %, about 0.5 to about 2 wt. %, about 1 to about 10 wt. %,about 1 to about 9 wt. %, about 1 to about 8 wt. %, about 1 to about 7wt. %, about 1 to about 6 wt. %, about 1 to about 5 wt. %, about 1 toabout 4 wt. %, about 1 to about 3 wt. %, about 2 to about 10 wt. %,about 2 to about 9 wt. %, about 2 to about 8 wt. %, about 2 to about 7wt. %, about 2 to about 6 wt. %, about 2 to about 5 wt. %, about 2 toabout 4 wt. %, about 3 to about 10 wt. %, about 3 to about 9 wt. %,about 3 to about 8 wt. %, about 3 to about 7 wt. %, about 3 to about 6wt. %, about 3 to about 5 wt. %, about 4 to about 10 wt. %, about 4 toabout 9 wt. %, about 4 to about 8 wt. %, about 4 to about 7 wt. %, about4 to about 6 wt. %, about 5 to about 10 wt. %, about 5 to about 9 wt. %,about 5 to about 8 wt. %, about 5 to about 7 wt. %, about 6 to about 10wt. %, about 6 to about 9 wt. %, about 6 to about 8 wt. %, about 7 toabout 10 wt. %, about 7 to about 9 wt. %, or about 8 to about 10 wt. %.

When the additives are described below by reference to individualcomponents used in the formulation, they will not necessarily be presentor identifiable as discrete entities in the final product but may bepresent as reaction products which are formed during the greasemanufacture or even its use. This will depend on the respectivechemistries of the ingredients, their stoichiometry, and thetemperatures encountered in the grease making process or during its use.It will also depend, naturally enough, on whether or not the species areadded as a pre-reacted additive package. For example, the acid aminephosphates may be added as discrete amines and acid phosphates but thesemay react to form a new entity in the final grease composition under theprocessing conditions used in the grease manufacture.

Viscosity Improver(s) or Modifier(s)

In any aspect or embodiment described herein, the composition of thepresent disclosure comprises at least one viscosity improver or modifier(e.g., 1, 2, 3, 4, 5, 6, or more viscosity improver or modifier). Theviscosity improver, viscosity modifier, or Viscosity Index (VI) modifierincreases the viscosity of the composition of the present disclosure atelevated temperatures, thereby increasing film thickness, and havinglimited effects on the viscosity of the composition of the presentdisclosure at low temperatures. In certain embodiments, the compositionof the present disclosure comprises at least one viscosity improver(e.g., 1, 2, 3, 4, 5, 6, or more viscosity improver(s)). Any viscosityimprover that is known or that becomes known in the art may be utilizedin the composition of the present disclosure. Exemplary viscosityimprovers include high molecular weight hydrocarbons, polyesters andviscosity index improver dispersants that function as both a viscosityindex improver and a dispersant. The molecular weight of these polymerscan range from about 1,000 to about 1,500,000 (e.g., about 20,000 toabout 1,200,000 or about 50,000 to about 1,000,000). In a particularembodiment, the molecular weights of these polymers can range from about1,000 to about 1,000,000 (e.g., about 1,200 to about 500,000 or about1,200 to about 5,000).

In certain embodiments, the viscosity improver is at least one of linearor star-shaped polymers of methacrylate, linear or star-shapedcopolymers of methacrylate, butadiene, olefins, alkylated styrenes,polyisobutylene, polymethacrylate (e.g., copolymers of various chainlength alkyl methacrylates), copolymers of ethylene and propylene,hydrogenated block copolymers of styrene and isoprene, or combinationsthereof. For example, the viscosity improver may includestyrene-isoprene or styrene-butadiene based polymers of about 50,000 toabout 200,000 molecular weight.

Olefin copolymers are commercially available from Chevron OroniteCompany LLC under the trade designation “PARATONE®” (such as “PARATONE®8921” and “PARATONE® 8941”); from Afton Chemical Corporation under thetrade designation “HiTEC®” (such as “HiTEC® 5850B”); and from TheLubrizol Corporation under the trade designation “Lubrizol® 7067C”.Hydrogenated polyisoprene star polymers are commercially available fromInfineum International Limited, e.g., under the trade designation“SV200” and “SV600”. Hydrogenated diene-styrene block copolymers arecommercially available from Infineum International Limited, e.g., underthe trade designation “SV 50”.

The polymethacrylate or polyacrylate polymers can be linear polymerswhich are available from Evnoik Industries under the trade designation“Viscoplex®” (e.g., Viscoplex 6-954) or star polymers which areavailable from Lubrizol Corporation under the trade designation Asteric™(e.g., Lubrizol 87708 and Lubrizol 87725).

Illustrative vinyl aromatic-containing polymers useful in the presentdisclosure may be derived predominantly from vinyl aromatic hydrocarbonmonomer. Illustrative vinyl aromatic-containing copolymers useful in thepresent disclosure may be represented by the following formula:

A-B

wherein: A is a polymeric block derived predominantly from vinylaromatic hydrocarbon monomer and B is a polymeric block derivedpredominantly from conjugated diene monomer.

Although their presence is not required to obtain the benefit of thecomposition of the present disclosure, viscosity modifiers may be usedin an amount of less than about 10 weight percent (e.g. less than about7 weight percent or less than about 4 weight percent). In certainembodiments, the viscosity improver is present in an amount less than 2weight percent, less than about 1 weight percent, or less than about 0.5weight percent, based on the total weight of the composition of thepresent disclosure. Viscosity modifiers are generally added asconcentrates, in large amounts of diluent oil.

As used herein, the viscosity modifier concentrations are given on an“as delivered” basis. The active polymer may be delivered with a diluentoil. The “as delivered” viscosity modifier may contain from about 20weight percent to about 75 weight percent of an active polymer forpolymethacrylate or polyacrylate polymers, or from about 8 weightpercent to about 20 weight percent of an active polymer for olefincopolymers, hydrogenated polyisoprene star polymers, or hydrogenateddiene-styrene block copolymers, in the “as delivered” polymerconcentrate.

Antioxidant(s)

In any aspect or embodiment described herein, the composition of thepresent disclosure comprises at least one antioxidant (e.g., 1, 2, 3, 4,5, 6, or more antioxidant(s)). The antioxidant(s) may be added to retardthe oxidative degradation of the composition in storage or duringservice. Such degradation may result in deposits on metal surfaces, thepresence of sludge, or a viscosity increase in the lubricant. Oneskilled in the art knows a wide variety of oxidation inhibitors that areuseful in lubricating oil compositions. See, Klamann in Lubricants andRelated Products, op cite, and U.S. Pat. Nos. 4,798,684 and 5,084,197,for example. Any antioxidant that is known or that becomes known in theart may be utilized in the composition of the present disclosure.

Two general types of oxidation inhibitors are those that react with theinitiators, peroxy radicals, and hydroperoxides to form inactivecompounds, and those that decompose these materials to form less activecompounds. Examples are hindered (alkylated) phenols, e.g.6-di(tert-butyl)-4-methylphenol [2,6-di(tert-butyl)-p-cresol, DBPC], andaromatic amines, e.g. N-phenyl-α-naphthalamine. These oxidationinhibitors are used in turbine, circulation, and hydraulic oils that areintended for extended service.

The antioxidant or antioxidants may be present in an amount equal to orless than about 6 wt. %, equal to or less than about 5.75 wt. %, equalto or less than about 5.5 wt. %, equal to or less than about 5.25 wt. %,equal to or less than about 5 wt. %, equal to or less than about 4.75wt. %, equal to or less than about 4.5 wt. %, equal to or less thanabout 4.25 wt. %, equal to or less than about 4 wt. %, equal to or lessthan about 3.75 wt. %, equal to or less than about 3.5 wt. %, equal toor less than about 3.25 wt. %, equal to or less than about 3 wt. %,equal to or less than about 2.75 wt. %, equal to or less than about 2.5wt. %, equal to or less than about 2.25 wt. %, equal to or less thanabout 2 wt. %, equal to or less than about 1.75 wt. %, equal to or lessthan about 1.5 wt. %, equal to or less than about 1.25 wt. %, equal toor less than about 1 wt. %, equal to or less than about 0.75 wt. %,equal to or less than about 0.50 wt. %, or equal to or less than about0.25 wt. % on an as-received basis. For example, the antioxidant orantioxidants may be present in an amount of about 0.1 wt. % to about 6wt. %, about 0.1 wt. % to about 5 wt. %, about 0.1 wt. % to about 4 wt.%, about 0.1 wt. % to about 3 wt. %, about 0.1 wt. % to about 2 wt. %,about 0.1 wt. % to about 1.5 wt. %, about 0.1 wt. % to about 1 wt. %,about 0.1 wt. % to about 0.75 wt. %, about 0.1 wt. % to about 0.5 wt. %,about 0.2 wt. % to about 6 wt. %, about 0.2 wt. % to about 5 wt. %,about 0.2 wt. % to about 4 wt. %, about 0.2 wt. % to about 3 wt. %,about 0.2 wt. % to about 2 wt. %, about 0.2 wt. % to about 1.5 wt. %,about 0.2 wt. % to about 1 wt. %, about 0.2 wt. % to about 0.75 wt. %,about 0.2 wt. % to about 0.5 wt. %, about 0.3 wt. % to about 6 wt. %,about 0.3 wt. % to about 5 wt. %, about 0.3 wt. % to about 4 wt. %,about 0.3 wt. % to about 3 wt. %, about 0.3 wt. % to about 2 wt. %,about 0.3 wt. % to about 1.5 wt. %, about 0.3 wt. % to about 1 wt. %,about 0.3 wt. % to about 0.75 wt. %, about 0.3 wt. % to about 0.5 wt. %,about 0.5 wt. % to about 6 wt. %, about 0.5 wt. % to about 5 wt. %,about 0.5 wt. % to about 4 wt. %, about 0.5 wt. % to about 3 wt. %,about 0.5 wt. % to about 2 wt. % about 0.5 wt. % to about 1.5 wt. %,about 0.5 wt. % to about 1 wt. %, about 0.5 wt. % to about 0.75 wt. %,about 0.5 wt. % to about 0.5 wt. %, about 1 wt. % to about 6 wt. %,about 1 wt. % to about 5 wt. %, about 1 wt. % to about 4 wt. %, about 1wt. % to about 3 wt. %, about 2 wt. % to about 6 wt. %, about 2 wt. % toabout 5 wt. %, about 2 wt. % to about 4 wt. %, about 3 wt. % to about 6wt. %, about 3 wt. % to about 5 wt. %, about 4 wt. % to about 6 wt. %,or about 5 wt. % to about 6 wt. % on an as-received basis.

The below discussion of phenolic antioxidants is presented only by wayof example, and is not limiting on the type of phenolic antioxidantsthat can be utilized in the composition of the present disclosure.

Useful antioxidants include hindered phenols. These phenolicantioxidants may be ashless (metal-free) phenolic compounds or neutralor basic metal salts of certain phenolic compounds. In an embodiment,the phenolic antioxidant compounds or compounds are hindered phenolicswhich are the ones which contain a sterically hindered hydroxyl group,such as those that are derivatives of dihydroxy aryl compounds in whichthe hydroxyl groups are in the o- or p-position to each other. Incertain embodiments, the phenolic antioxidant or antioxidants arehindered phenols substituted with C6+ alkyl groups and the alkylenecoupled derivatives of these hindered phenols. Examples of phenolicmaterials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octylphenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol;2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl phenol; and2-methyl-6-t-butyl-4-dodecyl phenol. Other useful hindered mono-phenolicantioxidants may include for example hindered 2,6-di-alkyl-phenolicproprionic ester derivatives. Bis-phenolic antioxidants may also beadvantageously used in combination with the composition of the presentdisclosure. Examples of ortho-coupled phenols include:2,2′-bis(4-heptyl-6-t-butyl-phenol); 2,2′-bis(4-octyl-6-t-butyl-phenol);and 2,2′-bis(4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenolsinclude for example 4,4′-bis(2,6-di-t-butyl phenol) and4,4′-methylene-bis(2,6-di-t-butyl phenol).

Further examples of phenol-based antioxidants include 2-t-butylphenol,2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol,2,4-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol,2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol,2,5-di-t-butylhydroquinone (manufactured by the Kawaguchi Kagaku Co.under trade designation “Antage DBH”), 2,6-di-t-butylphenol and2,6-di-t-butyl-4-alkylphenols such as 2,6-di-t-butyl-4-methylphenol and2,6-di-t-butyl-4-ethylphenol; 2,6-di-t-butyl-4-alkoxyphenols such as2,6-di-t-butyl-4-methoxyphenol and 2,6-di-t-butyl-4-ethoxyphenol,3,5-di-t-butyl-4-hydroxybenzylmercaptoocty-1 acetate,alkyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionates such asn-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured bythe Yoshitomi Seiyaku Co. under the trade designation “Yonox SS”),n-dodecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and2′-ethylhexyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate;2,6-di-t-butyl-alpha-dimethylamino-p-cresol,2,2′-methylenebis(4-alkyl-6-t-butylphenol) compounds such as2,2′-methylenebis(4-methyl-6-t-butylphe-nol) (manufactured by theKawaguchi Kagaku Co. under the trade designation “Antage W-400”) and2,2′-methylenebis(4-ethyl-6-t-butylphenol) (manufactured by theKawaguchi Kagaku Co. under the trade designation “Antage W-500”);bisphenols such as 4,4′-butylidenebis(3-methyl-6-t-butyl-phenol)(manufactured by the Kawaguchi Kagaku Co. under the trade designation“Antage W-300”), and 4,4′-methylenebis(2,6-di-t-butylphenol)(manufactured by Laporte Performance Chemicals under the tradedesignation “Ionox 220AH”).

Other examples of phenol-based antioxidants include4,4′-bis(2,6-di-t-butylphenol), 2,2-(di-p-hydroxyphenyl)propane(Bisphenol A), 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane,4,4′-cyclohexylidenebis(2,6-di-t-butylphenol), hexamethylene glycolbis[3, (3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by theCiba Specialty Chemicals Co. under the trade designation “IrganoxL109”), triethylene glycolbis[3-(3-t-butyl-4-hydrox-y-5-methylphenyl)propionate] (manufactured bythe Yoshitomi Seiyaku Co. under the trade designation “Tominox 917”),2,2′-thio[diethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate](manufacturedby the Ciba Specialty Chemicals Co. under the trade designation “IrganoxL115”), 3,9-bis{1,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionylo-xy]ethyl}2,4,8,10-tetraoxaspiro[5,5]undecane(manufactured by the Sumitomo Kagaku Co. under the trade designation“Sumilizer GA80”) and 4,4′-thiobis(3-methyl-6-t-butylphenol)(manufactured by the Kawaguchi Kagaku Co. under the trade designation“Antage RC”), 2,2′-thiobis(4,6-di-t-butylresorcinol); polyphenols, suchastetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionato]methane(manufactured by the Ciba Specialty Chemicals Co. under the tradedesignation “Irganox L101”),1,1,3-tris(2-methyl-4-hydroxy-5-t-butylpheny-1)butane (manufactured bythe Yoshitomi Seiyaku Co. under the trade designation “Yoshinox 930”),1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene(manufactured by Ciba Specialty Chemicals under the trade designation“Irganox 330”), bis[3,3′-bis(4′-hydroxy-3′-t-butylpheny-1)butyric acid]glycol ester,2-(3′,5′-di-t-butyl-4-hydroxyphenyl)-methyl-4-(2″,4″-di-t-butyl-338-hydroxyphenyl)methyl-6-t-butylphenoland 2,6-bis(2′-hydroxy-3′-t-butyl-5′-methylbenzyl)-4-methylphenol; andphenol/aldehyde condensates, such as the condensates of p-t-butylphenoland formaldehyde and the condensates of p-t-butylphenol andacetaldehyde.

The phenolic antioxidant or phenolic type antioxidant include sulfurizedand non-sulfurized phenolic antioxidants. Phenolic antioxidants includecompounds having one or more than one hydroxyl group bound to anaromatic ring which may itself be mononuclear (e.g., benzyl) orpoly-nuclear (e.g., naphthyl and spiro aromatic compounds). Thus, phenoltype antioxidants include phenol per se, catechol, resorcinol,hydroquinone, naphthol, etc., as well as alkyl or alkenyl and sulfurizedalkyl or alkenyl derivatives thereof, and bisphenol type compoundsincluding such bi-phenol compounds linked by alkylene bridges sulfuricbridges or oxygen bridges. Alkyl phenols may include mono- andpoly-alkyl or alkenyl phenols, the alkyl or alkenyl group containingfrom about 3 to about 100 carbons (e.g., about 4 to about 50 carbons)and sulfurized derivatives thereof. The number of alkyl or alkenylgroups present in the aromatic ring may range from 1 up to the availableunsatisfied valences of the aromatic ring remaining after counting thenumber ofhydroxyl groups bound to the aromatic ring.

For example, the phenolic antioxidant may be represented by thefollowing formula:

(R)_(x)—Ar—(OH)_(y)

wherein: Ar is selected from the group consisting of:

wherein: R is a C₃-C₁₀₀ alkyl or alkenyl group, a sulfur substitutedalkyl or alkenyl group (e.g., a C₄-C₅₀ alkyl or alkenyl group or sulfursubstituted alkyl or alkenyl group, a C₃-C₁₀₀ alkyl or sulfursubstituted alkyl group, or a C₄-C₅₀ alkyl group); R^(G) is a C₁-C₁₀₀alkylene or sulfur substituted alkylene group (e.g., a C₂-C₅₀ alkyleneor sulfur substituted alkylene group or a C₂-C₂ alkylene or sulfursubstituted alkylene group); y is at least 1 to up to the availablevalences of Ar; x ranges from 0 to up to the available valances of Ar-y;z ranges from 1 to 10; n ranges from 0 to 20; m is 0 to 4; and p is 0 or1.

In certain embodiments, at least one of: R is C₄-C₅₀ alkyl group, R^(g)is a C₂-C₂₀ alkylene or sulfur substituted alkylene group, y ranges from1 to 3, x ranges from 0 to 3, z ranges from 1 to 4, n ranges from 0 to5, p is 0, or a combination thereof.

In particular embodiments, the phenolic antioxidant includes hinderedphenolics and phenolic esters that contain a sterically hinderedhydroxyl group. For example, the phenolic antioxidant can includederivatives of dihydroxy aryl compounds in which the hydroxyl groups arein the o- or p-position to each other. The phenolic antioxidant mayinclude the hindered phenols substituted with C₁+ alkyl groups and thealkylene coupled derivatives of these hindered phenols, such as:2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecylphenol; 2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol;2-methyl-6-t-butyl-4-heptyl phenol; 2-methyl-6-t-butyl-4-dodecyl phenol;2,6-di-t-butyl-4 methyl phenol; 2,6-di-t-butyl-4-ethyl phenol;2,6-di-t-butyl 4 alkoxy phenol; and/or

In certain embodiments, the phenolic type antioxidant is at least one ofEthanox® 4710, Irganox® 1076, Irganox® L1035, Irganox® 1010, Irganox®L109, Irganox® L118, Irganox® L135, or a combination thereof.

The phenolic antioxidant or antioxidants may be present in an amount ofabout 0.05 wt. % to about 3 wt. %, about 0.05 wt. % to about 2.5 wt. %,about 0.05 wt. % to about 2 wt. %, about 0.05 wt. % to about 1.5 wt. %,about 0.05 wt. % to about 1 wt. %, about 0.05 wt. % to about 0.75 wt. %,about 0.05 wt. % to about 0.5 wt. %, about 0.05 wt. % to about 0.3 wt.%, about 0.1 wt. % to about 3 wt. %, about 0.1 wt. % to about 2.5 wt. %,about 0.1 wt. % to about 2 wt. %, about 0.1 wt. % to about 1.5 wt. %,about 0.1 wt. % to about 1 wt. %, about 0.1 wt. % to about 0.75 wt. %,about 0.1 wt. % to about 0.5 wt. %, about 0.1 wt. % to about 0.3 wt. %,about 0.5 wt. % to about 3 wt. %, about 0.5 wt. % to about 2.5 wt. %,about 0.5 wt. % to about 2 wt. %, about 0.5 wt. % to about 1.5 wt. %,about 0.5 wt. % to about 1 wt. %, about 1 wt. % to about 3 wt. %, about1 wt. % to about 2.5 wt. %, about 1 wt. % to about 2 wt. %, about 1 wt.% to about 1.75 wt. %, about 1 wt. % to about 1.5 wt. %, about 1.5 wt. %to about 3 wt. %, about 1.5 wt. % to about 2.5 wt. %, about 1.5 wt. % toabout 2 wt. %, about 2 wt. % to about 3 wt. %, about 2 wt. % to about2.5 wt. %, or about 2.5 wt. % to about 3 wt. %, on an as-received basis.

Effective amounts of one or more catalytic antioxidants may be used. Thecatalytic antioxidants comprise an effective amount of a) one or moreoil soluble polymetal organic compounds; and, effective amounts of b)one or more substituted N,N′-diaryl-o-phenylenediamine compounds or c)one or more hindered phenol compounds; or a combination of both b) andc). Catalytic antioxidants are more fully described in U.S. Pat. No.8,048,833, which is incorporated herein by reference in its entirety.

Non-phenolic oxidation inhibitors that may be used in the composition ofthe present disclosure include aromatic amine antioxidants, which may beused either as such or in combination with phenolic antioxidants.

An exemplary aromatic amine antioxidant includes alkylated andnon-alkylated aromatic amines, such as aromatic monoamines of theformula

R¹R²R³N

wherein: R¹ is an aliphatic, aromatic or substituted aromatic group; R²is an aromatic or a substituted aromatic group; R³ is H, alkyl, aryl orR⁴S(O)xR⁵; R⁴ is an alkylene, alkenylene, or aralkylene group; R⁵ is ahigher alkyl group, or an alkenyl, aryl, or alkaryl group; and x is 0, 1or 2.

The aliphatic group R¹ may contain from 1 to about 20 carbon atoms (e.g.from about 6 to 12 carbon atoms). The aliphatic group may be a saturatedaliphatic group. In certain embodiments, both R¹ and R² are aromatic orsubstituted aromatic groups, and the aromatic group may be a fused ringaromatic group such as naphthyl. Aromatic groups R¹ and R² may be joinedtogether with other groups such as S.

The aminic antioxidant may be an aromatic amine antioxidant, such as aphenyl-α-naphthyl amine (e.g., Irganox® L06) which is described by thefollowing chemical structure:

wherein: R^(z) is hydrogen or a C₁ to C₁₄ linear or C₃ to C₁₄ branchedalkyl group; and n is an integer ranging from 1 to 5 (e.g. 1).

In certain embodiments, at least one of: R^(z) is C₁ to C₁₀ linear or C₃to C₁₀ branched alkyl group; n is 1; or a combination thereof.

In another embodiment, R^(z) is a linear or branched C₆ to C₈.

In certain embodiments, the aromatic amine antioxidant can have at least6 carbon atoms substituted with an alkyl groups. Examples of aliphaticgroups include hexyl, heptyl, octyl, nonyl, and decyl. In anembodiments, the aliphatic groups will not contain more than about 14carbon atoms. Additional amine antioxidants include diphenylamines,phenyl naphthylamines, phenothiazines, imidodibenzyls, and diphenylphenylene diamines. In a particular embodiment, a mixture of two or more(e.g., 2, 3, 4, 5, or more) aromatic amine antioxidants are present inthe composition of the present disclosure. Polymeric amine antioxidantscan also be used. Particular examples of aromatic amine antioxidantsuseful in the composition of the present disclosure include:p,p′-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine;phenyl-alphanaphthylamine; and p-octylphenyl-alpha-naphthylamine.

Further examples of amine-based antioxidants includedialkyldiphenylamines, such as p,p′-dioctyldiphenylamine (manufacturedby the Seiko Kagaku Co. under the trade designation “Nonflex OD-3”),p,p′-di-alpha-methylbenzyl-diphenylamine andN-p-butylphenyl-N-p′-octylphenylamine; monoalkyldiphenylamines, such asmono-t-butyldiphenylamine, and monooctyldiphenylamine;bis(dialkylphenyl)amines such as di(2,4-diethylphenyl)amine anddi(2-ethyl-4-nonylphenyl)amine; alkylphenyl-1-naphthylamines, such asoctylphenyl-1-naphthylamine and N-t-dodecylphenyl-1-naphthylamine;arylnaphthylamines, such as 1-naphthylamine, phenyl-1-naphthylamine,phenyl-2-naphthylamine, N-hexylphenyl-2-naphthylamine andN-octylphenyl-2-naphthylamine, phenylenediamines such asN,N′-diisopropyl-p-phenylenediamine andN,N′-diphenyl-p-phenylenediamine, and phenothiazines such asphenothiazine (manufactured by the Hodogaya Kagaku Co.: Phenothiazine)and 3,7-dioctylphenothiazine.

A sulfur-containing antioxidant may be any and every antioxidantcontaining sulfur, for example, including dialkyl thiodipropionates suchas dilauryl thiodipropionate and distearyl thiodipropionate,dialkyldithiocarbamic acid derivatives (excluding metal salts),bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide, mercaptobenzothiazole,reaction products of phosphorus pentoxide and olefins, and dicetylsulfide. For example, the sulfur-containing antioxidant is a dialkylthiodipropionate, such as dilauryl thiodipropionate and distearylthiodipropionate.

Additional examples of sulphur-based antioxidants includedialkylsulphides, such as didodecylsulphide and dioctadecylsulphide;thiodipropionic acid esters, such as didodecyl thiodipropionate,dioctadecyl thiodipropionate, dimyristyl thiodipropionate anddodecyloctadecyl thiodipropionate, and 2-mercaptobenzimidazole. In anembodiment, the antioxidant is a sulfurized alkyl phenols, or an alkalior alkaline earth metal salt thereof.

In certain embodiments, the composition of the present disclosureincludes at least one aminic antioxidant (e.g., 1, 2, 3, 4, 5, or more)present in an amount equal to or less than about 6 wt. %, equal to orless than about 5.75 wt. %, equal to or less than about 5.5 wt. %, equalto or less than about 5.25 wt. %, equal to or less than about 5 wt. %,equal to or less than about 4.75 wt. %, equal to or less than about 4.5wt. %, equal to or less than about 4.25 wt. %, equal to or less thanabout 4 wt. %, equal to or less than about 3.75 wt. %, equal to or lessthan about 3.5 wt. %, equal to or less than about 3.25 wt. %, equal toor less than about 3 wt. %, equal to or less than about 2.75 wt. %,equal to or less than about 2.5 wt. %, equal to or less than about 2.25wt. %, equal to or less than about 2 wt. %, equal to or less than about1.75 wt. %, equal to or less than about 1.5 wt. %, equal to or less thanabout 1.25 wt. %, equal to or less than about 1 wt. %, equal to or lessthan about 0.75 wt. %, equal to or less than about 0.50 wt. %, or equalto or less than about 0.25 wt. % on an as-received basis. For example,the aminic antioxidant or antioxidants may be present in an amount ofabout 0.1 wt. % to about 6 wt. %, about 0.1 wt. % to about 5 wt. %,about 0.1 wt. % to about 4 wt. %, about 0.1 wt. % to about 3 wt. %,about 0.1 wt. % to about 2 wt. %, about 0.1 wt. % to about 1.5 wt. %,about 0.1 wt. % to about 1 wt. %, about 0.1 wt. % to about 0.75 wt. %,about 0.1 wt. % to about 0.5 wt. %, about 0.2 wt. % to about 6 wt. %,about 0.2 wt. % to about 5 wt. %, about 0.2 wt. % to about 4 wt. %,about 0.2 wt. % to about 3 wt. %, about 0.2 wt. % to about 2 wt. %,about 0.2 wt. % to about 1.5 wt. %, about 0.2 wt. % to about 1 wt. %,about 0.2 wt. % to about 0.75 wt. %, about 0.2 wt. % to about 0.5 wt. %,about 0.3 wt. % to about 6 wt. %, about 0.3 wt. % to about 5 wt. %,about 0.3 wt. % to about 4 wt. %, about 0.3 wt. % to about 3 wt. %,about 0.3 wt. % to about 2 wt. %, about 0.3 wt. % to about 1.5 wt. %,about 0.3 wt. % to about 1 wt. %, about 0.3 wt. % to about 0.75 wt. %,about 0.3 wt. % to about 0.5 wt. %, about 0.5 wt. % to about 6 wt. %,about 0.5 wt. % to about 5 wt. %, about 0.5 wt. % to about 4 wt. %,about 0.5 wt. % to about 3 wt. %, about 0.5 wt. % to about 2 wt. %,about 0.5 wt. % to about 1.5 wt. %, about 0.5 wt. % to about 1 wt. %,about 0.5 wt. % to about 0.75 wt. %, about 0.5 wt. % to about 0.5 wt. %,about 1 wt. % to about 6 wt. %, about 1 wt. % to about 5 wt. %, about 1wt. % to about 4 wt. %, about 1 wt. % to about 3 wt. %, about 2 wt. % toabout 6 wt. %, about 2 wt. % to about 5 wt. %, about 2 wt. % to about 4wt. %, about 3 wt. % to about 6 wt. %, about 3 wt. % to about 5 wt. %,about 4 wt. % to about 6 wt. %, or about 5 wt. % to about 6 wt. % on anas-received basis.

Other oxidation inhibitors that have proven useful in compositions ofthe present disclosure are chlorinated aliphatic hydrocarbons such aschlorinated wax; organic sulfides and polysulfides such as benzyldisulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurizedmethyl ester of oleic acid, sulfurized alkylphenol, sulfurizeddipentene, and sulfurized terpene; phosphosulfurized hydrocarbons suchas the reaction product of a phosphorus sulfide with turpentine ormethyl oleate, phosphorus esters including principally dihydrocarbon andtrihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite,dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenylphosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthylphosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecularweight 500)-substituted phenyl phosphite, diisobutyl-substituted phenylphosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate,and barium heptylphenyl dithiocarbamate; Group II metalphosphorodithioates such as zinc dicyclohexylphosphorodithioate, zincdioctylphosphorodithioate, barium di(heptylphenyl)(phosphorodithioate,cadmium dinonylphosphorodithioate, and the reaction of phosphoruspentasulfide with an equimolar mixture of isopropyl alcohol,4-methyl-2-pentanol, and n-hexyl alcohol.

Another class of antioxidants which may be used in the lubricating oilcompositions disclosed herein are oil soluble copper compounds. Any oilsoluble suitable copper compound may be blended into the composition ofthe present disclosure. Examples of suitable copper antioxidants includecopper dihydrocarbyl thio- or dithio-phosphates and copper salts ofcarboxylic acid (naturally occurring or synthetic). Other suitablecopper salts include copper dithiacarbamates, sulphonates, phenates, andacetylacetonates. Basic, neutral, or acidic copper Cu(I) and or Cu(II)salts derived from alkenyl succinic acids or anhydrides are known to beparticularly useful.

In an embodiment, the antioxidant includes hindered phenols, arylamines,or a combination thereof. These antioxidants may be used individually bytype or in combination with one another.

Pour Point Depressant(s)

In any aspect or embodiment described herein, the composition of thepresent disclosure comprises at least one (e.g., 1, 2, 3, 4, 5, or 6, ormore) pour point depressant or a lube oil flow improver. Pour pointdepressant may be added to lower the minimum temperature at which thefluid will flow or can be poured. Any pour point depressant or lube oilflow improved that is known or that becomes known in the art may beutilized in the composition of the present disclosure. In certainembodiments, the pour point depressant includes at least one (e.g., 1,2, 3, or 4 or more) pour point depressant or lube oil flow improver,such as at least one of alkylated naphthalenes polymethacrylates (e.g.,copolymers of various chain length alkyl methacrylates), polyacrylates,polyarylamides, condensation products of haloparaffin waxes and aromaticcompounds, vinyl carboxylate polymers, terpolymers of dialkylfumarates,vinyl esters of fatty acids, allyl vinyl ethers, or combinationsthereof. U.S. Pat. Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501;2,655, 479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describeuseful pour point depressants and/or the preparation thereof.

The pour point depressant or depressants may be present in an amountequal to or less than about 5 wt. %, for example about 0.01 to about 1.5wt. %. For example, the pour point depressant or depressants may bepresent in an amount equal to or less than about 5 wt. %, equal to orless than about 4.75 wt. %, equal to or less than about 4.5 wt. %, equalto or less than about 4.25 wt. %, equal to or less than about 4 wt. %,equal to or less than about 3.75 wt. %, equal to or less than about 3.5wt. %, equal to or less than about 3.25 wt. %, equal to or less thanabout 3 wt. %, equal to or less than about 2.75 wt. %, equal to or lessthan about 2.5 wt. %, equal to or less than about 2.25 wt. %, equal toor less than about 2 wt. %, equal to or less than about 1.75 wt. %,equal to or less than about 1.5 wt. %, equal to or less than about 1.25wt. %, equal to or less than about 1 wt. %, equal to or less than about0.75 wt. %, equal to or less than about 0.50 wt. %, or equal to or lessthan about 0.25 wt. % of the composition of the present disclosure. Forexample, the pour point depressant or depressants may be present in anamount of about 0.1 wt. % to about 5 wt. %, about 0.1 wt. % to about 4wt. %, about 0.1 wt. % to about 3 wt. %, about 0.1 wt. % to about 2 wt.%, about 0.1 wt. % to about 1.5 wt. %, about 0.1 wt. % to about 1 wt. %,about 0.1 wt. % to about 0.75 wt. %, about 0.1 wt. % to about 0.5 wt. %,about 0.2 wt. % to about 5 wt. %, about 0.2 wt. % to about 4 wt. %,about 0.2 wt. % to about 3 wt. %, about 0.2 wt. % to about 2 wt. %,about 0.2 wt. % to about 1.5 wt. %, about 0.2 wt. % to about 1 wt. %,about 0.2 wt. % to about 0.75 wt. %, about 0.2 wt. % to about 0.5 wt. %,about 0.3 wt. % to about 5 wt. %, about 0.3 wt. % to about 4 wt. %,about 0.3 wt. % to about 3 wt. %, about 0.3 wt. % to about 2 wt. %,about 0.3 wt. % to about 1.5 wt. %, about 0.3 wt. % to about 1 wt. %,about 0.3 wt. % to about 0.75 wt. %, about 0.3 wt. % to about 0.5 wt. %,about 0.5 wt. % to about 5 wt. %, about 0.5 wt. % to about 4 wt. %,about 0.5 wt. % to about 3 wt. %, about 0.5 wt. % to about 2 wt. %,about 0.5 wt. % to about 1.5 wt. %, about 0.5 wt. % to about 1 wt. %,about 0.5 wt. % to about 0.75 wt. %, about 0.5 wt. % to about 0.5 wt. %,about 1 wt. % to about 5 wt. %, about 1 wt. % to about 4 wt. %, about 1wt. % to about 3 wt. %, about 2 wt. % to about 5 wt. %, about 2 wt. % toabout 4 wt. %, or about 3 wt. % to about 5 wt. % of the composition ofthe present disclosure.

Seal Compatibility Agent(s)

In other embodiments, the composition comprises of the presentdisclosure at least one (e.g., 1, 2, 3, 4, or more) seal compatibilityagent. The seal compatibility agent(s) may be added to help swellelastomeric seals by causing a chemical reaction in the fluid orphysical change in the elastomer. Any seal compatibility agent that isknown or that becomes know may be utilized in the composition of thepresent disclosure. For example, the seal compatibility agent or agentsmay include at least one of organic phosphates, aromatic esters,aromatic hydrocarbons, esters (e.g. butylbenzyl phthalate), polybutenylsuccinic anhydride, or sulfolane-type seal swell agents (e.g. Lubrizol730-type seal swell additives), or combinations thereof. Although theirpresence is not required to obtain the benefit of the presentdisclosure, seal compatibility additives may be present in an amount ofzero to about 3 weight percent (e.g., about 0.01 to about 2 weightpercent) of the composition of the present disclosure.

Demulsifier(s)

In any aspect or embodiment described herein, the composition of thepresent disclosure comprises at least one (e.g., 1, 2, 3, or 4, or more)demulsifier. The demulsifier may be added to separate emulsions (e.g.,water-in-oil). Any demulsifier that is known or that becomes know may beutilized in the composition of the present disclosure. An illustrativedemulsifying component is described in EP-A-330,522. This exemplarydemulsifying agent is obtained by reacting an alkylene oxide with anadduct obtained by reaction of a bis-epoxide with a polyhydric alcohol.Demulsifiers are commercially available and may be used in conventionalminor amounts along with other additives such as antifoam agents.Although their presence is not required to obtain the benefit of thepresent disclosure, the emulsifier or emulsifiers may be present acombined amount less than 1 weight percent (e.g. less than 0.1 weightpercent).

In certain embodiments, the demulsifying agent includes at least one ofalkoxylated phenols, phenol-formaldehyde resins, synthetic alkylarylsulfonates (such as metallic dinonylnaphthalene sulfonates), or acombination thereof. In an embodiment, a demulsifing agent is apredominant amount of a water-soluble polyoxyalkylene glycol having apre-selected molecular weight of any value in the range of between about450 and about 5000 or more. In an embodiment, the water solublepolyoxyalkylene glycol demulsifier may also be one produced fromalkoxylation of n-butanol with a mixture of alkylene oxides to form arandom alkoxylated product.

Polyoxyalkylene glycols useful in the present disclosure may be producedby a well-known process for preparing polyalkylene oxide having hydroxylend-groups by subjecting an alcohol or a glycol ether and one or morealkylene oxide monomers, such as ethylene oxide, butylene oxide, orpropylene oxide, to form block copolymers in addition polymerization,while employing a strong base, such as potassium hydroxide as acatalyst. In such a process, the polymerization is commonly carried outunder a catalytic concentration of about 0.3 to about 1.0% by mole ofpotassium hydroxide to the monomer(s) and at high temperature of about100° C. to about 160° C. It is well known that the catalyst potassiumhydroxide is, for the most part, bonded to the chain-end of the producedpolyalkylene oxide in a form of alkoxide in the polymer solution soobtained.

The soluble polyoxyalkylene glycol emulsifier(s) useful in thecompositions of the present disclosure may also be one produced fromalkoxylation of n-butanol with a mixture of alkylene oxides to form arandom alkoxylated product.

Corrosion Inhibitor or Anti-Rust Additive

In any aspect or embodiment, the composition of the present disclosurecomprises at least one (e.g. 1, 2, 3, 4, or more) corrosion inhibitor oranti-rust additive. The corrosion inhibitor or anti-rust additive may beadded to protect lubricated metal surfaces against chemical attack bywater or other contaminants. A wide variety of corrosion inhibitors arecommercially available, and any corrosion inhibitor or anti-rustadditive that is known or that becomes know may be utilized in thecomposition of the present disclosure. In an embodiment, the corrosioninhibitor can be a polar compound that wets the metal surface protectingit with a film of oil. In another embodiment, the anti-rust additive mayabsorb water by incorporating it in a water-in-oil emulsion so that onlythe oil touches the surface. In yet a further embodiment, the corrosioninhibitor chemically adheres to the metal to produce a non-reactivesurface. In certain embodiments, the anti-rust additive or corrosioninhibitor includes at least one zinc dithiophosphates, metal phenolates,basic metal sulfonates, a fatty acid, a fatty acid mixture, amines, or acombination thereof.

Antirust additives may include (short-chain) alkenyl succinic acids,partial esters thereof and nitrogen-containing derivatives thereof; andsynthetic alkarylsulfonates, such as metal dinonylnaphthalenesulfonates. Antirust agents include, for example, monocarboxylic acidswhich have from 8 to 30 carbon atoms, alkyl or alkenyl succinates orpartial esters thereof, hydroxy-fatty acids, which have from 12 to 30carbon atoms and derivatives thereof, sarcosines which have from 8 to 24carbon atoms and derivatives thereof, amino acids and derivativesthereof, naphthenic acid and derivatives thereof, lanolin fatty acid,mercapto-fatty acids, and/or paraffin oxides.

Examples of monocarboxylic acids (C8-C30), include, for example,caprylic acid, pelargonic acid, decanoic acid, undecanoic acid, lauricacid, myristic acid, palmitic acid, stearic acid, arachic acid, behenicacid, cerotic acid, montanic acid, melissic acid, oleic acid, docosanicacid, erucic acid, eicosenic acid, beef tallow fatty acid, soy beanfatty acid, coconut oil fatty acid, linolic acid, linoleic acid, talloil fatty acid, 12-hydroxystearic acid, laurylsarcosinic acid,myritsylsarcosinic acid, palmitylsarcosinic acid, stearylsarcosinicacid, oleylsarcosinic acid, alkylated (C8-C20) phenoxyacetic acids,lanolin fatty acid, and C8-C24 mercapto-fatty acids.

Examples of polybasic carboxylic acids include, for example, the alkenyl(C10-C100) succinic acids indicated in CAS No. 27859-58-1 and esterderivatives thereof, dimer acid, N-acyl-N-alkyloxyalkyl aspartic acidesters (U.S. Pat. No. 5,275,749).

Examples of the alkylamines that function as antirust additives or asreaction products with the above carboxylates to give amides and thelike are represented by primary amines, such as laurylamine,coconut-amine, n-tridecylamine, myristylamine, n-pentadecylamine,palmitylamine, n-heptadecylamine, stearylamine, n-nonadecylamine,n-eicosylamine, n-heneicosylamine, n-docosylamine, n-tricosylamine,n-pentacosylamine, oleylamine, beef tallow-amine, hydrogenated beeftallow-amine and soy bean-amine. Examples of the secondary aminesinclude dilaurylamine, di-coconut-amine, di-n-tridecylamine,dimyristylamine, di-n-pentadecylamine, dipalmitylamine,di-n-pentadecylamine, distearylamine, di-n-nonadecylamine,di-n-eicosylamine, di-n-heneicosylamine, di-n-docosylamine,di-n-tricosylamine, di-n-pentacosyl-amine, dioleylamine, di-beeftallow-amine, di-hydrogenated beef tallow-amine and di-soy bean-amine.

Examples of the aforementioned N-alkylpolyalkyenediamines include:ethylenediamines, such as laurylethylenediamine, coconutethylenediamine, n-tridecylethylenediamine-, myristylethylenediamine,n-pentadecylethylenediamine, palmitylethylenediamine,n-heptadecylethylenediamine, stearylethylenediamine,n-nonadecylethylenediamine, n-eicosylethylenediamine,n-heneicosylethylenediamine, n-docosylethylendiamine,n-tricosylethylenediamine, n-pentacosylethylenediamine,oleylethylenediamine, beef tallow-ethylenediamine, hydrogenated beeftallow-ethylenediamine and soy bean-ethylenediamine; propylenediaminessuch as laurylpropylenediamine, coconut propylenediamine,n-tridecylpropylenediamine, myristylpropylenediamine,n-pentadecylpropylenediamine, palmitylpropylenediamine,n-heptadecylpropylenediamine, stearylpropylenediamine,n-nonadecylpropylenediamine, n-eicosylpropylenediamine,n-heneicosylpropylenediamine, n-docosylpropylendiamine,n-tricosylpropylenediamine, n-pentacosylpropylenediamine, diethylenetriamine (DETA) or triethylene tetramine (TETA), oleylpropylenediamine,beef tallow-propylenediamine, hydrogenated beef tallow-propylenediamineand soy bean-propylenediamine; butylenediamines such aslaurylbutylenediamine, coconut butylenediamine,n-tridecylbutylenediamine-myristylbutylenediamine,n-pentadecylbutylenediamine, stearylbutylenediamine,n-eicosylbutylenediamine, n-heneicosylbutylenediamine,n-docosylbutylendiamine, n-tricosylbutylenediamine,n-pentacosylbutylenediamine, oleylbutylenediamine, beeftallow-butylenediamine, hydrogenated beef tallow-butylenediamine and soybean butylenediamine; and pentylenediamines such aslaurylpentylenediamine, coconut pentylenediamine,myristylpentylenediamine, palmitylpentylenediamine,stearylpentylenediamine, oleyl-pentylenediamine, beeftallow-pentylenediamine, hydrogenated beef tallow-pentylenediamine andsoy bean pentylenediamine.

The corrosion inhibitor or anti-rust additive may be present in anamount equal to or less than about 5 wt. %, for example about 0.01 to 5wt. %, on an as-received basis. For example, the corrosion inhibitor maybe present in an amount equal to or less than 4 wt. %, equal or lessthan 3 wt. %, equal to or less than 2 wt. %, or equal to or less than 1wt. % on an as-received basis. By way of further example, the corrosioninhibitor may be present in an amount of about 0.01 to about 5 wt. %,about 0.01 to about 4 wt. %, about 0.01 to about 3 wt. %, about 0.01 toabout 2 wt. %, about 0.05 to about 5 wt. %, about 0.05 to about 4 wt. %,about 0.05 to about 3 wt. %, about 0.05 to about 2 wt. %, about 0.1 toabout 5 wt. %, about 0.1 to about 4 wt. %, about 0.1 to about 3 wt. %,about 0.1 to about 2 wt. %, about 1 to about 5 wt. %, about 1 to about 4wt. %, about 1 to about 3 wt. %, about 2 to about 5 wt. %, about 2 toabout 4 wt. %, or about 3 to about 5 wt. %, on an as-received basis.

Metal Passivator(s), Deactivator(s) and Corrosion Inhibitor(s)

In any aspect or embodiment, the composition of the present disclosurecomprises at least one (e.g. 1, 2, 3, 4, 5, or 6, or more) metalpassivator, deactivator, or corrosion inhibitor. This type of componentincludes 2,5-dimercapto-1,3,4-thiadiazoles and derivatives thereof,mercaptobenzothiazoles, alkyltriazoles and benzotriazoles. Examples ofdibasic acids useful as anti-corrosion agents, other than sebacic acids,which may be used in the present disclosure, are adipic acid, azelaicacid, dodecanedioic acid, 3-methyladipic acid, 3-nitrophthalic acid,1,10-decanedicarboxylic acid, and fumaric acid. The anti-corrosioncombination is a straight or branch-chained, saturated or unsaturatedmonocarboxylic acid or ester thereof which may optionally be sulphurizedin an amount up to 35% by weight. In an embodiment, the acid is a C4 toC22 straight chain unsaturated monocarboxylic acid. The monocarboxylicacid may be a sulphurized oleic acid. However, other suitable materialsare oleic acid itself, valeric acid and erucic acid. A component of theanti-corrosion combination is a triazole as previously defined. In anembodiment, the triazole is tolylotriazole, which may be included in thecompositions of the disclosure include triazoles, thiazoles and certaindiamine compounds which are useful as metal deactivators or metalpassivators. Examples include triazole, benzotriazole and substitutedbenzotriazoles, such as alkyl substituted derivatives. The alkylsubstituent may contain up to 1.5 carbon atoms, e.g. up to 8 carbonatoms. The triazoles may contain other substituents on the aromatic ringsuch as halogens, nitro, amino, mercapto, etc. Examples of suitablecompounds are benzotriazole and the tolyltriazoles, ethylbenzotriazoles,hexylbenzotriazoles, octylbenzotriazoles, chlorobenzotriazoles andnitrobenzotriazoles. In a particular embodiment, the compound isbenzotriazole and/or tolyltriazole.

Illustrative substituents include, for example, alkyl that is straightor branched chain, for example, methyl, ethyl, n-propyl, iso-propyl,n-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl,n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl orn-eicosyl; alkenyl that is straight or branched chain, for example,prop-2-enyl, but-2-enyl, 2-methyl-prop-2-enyl, pent-2-enyl,hexa-2,4-dienyl, dec-10-enyl or eicos-2-enyl; cycloalkyl that is, forexample, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, adamantyl orcyclododecyl; aralkyl that is, for example, benzyl, 2-phenylethyl,benzhydryl or naphthylmethyl; aryl that is, for example, phenyl ornaphthyl; heterocyclic group that is, for example, a morpholine,pyrrolidine, piperidine or a perhydroazepine ring; alkylene moietiesthat include, for example, methylene, ethylene, 1:2- or 1:3-propylene,1:4-butylene, 1:6-hexylene, 1:8-octylene, 1:10-decylene and1:12-dodecylene.

Illustrative arylene moieties include, for example, phenylene andnaphthylene. 1-(or 4)-(dimethylaminomethyl) triazole, 1-(or4)-(diethylaminomethyl) triazole, 1-(or 4)-(di-isopropylaminomethyl)triazole, 1-(or 4)-(di-n-butylaminomethyl) triazole, 1-(or4)-(di-n-hexylaminomethyl) triazole, 1-(or 4)-(di-isooctylaminomethyl)triazole, 1-(or 4)-(di-(2-ethylhexyl)aminomethyl) triazole, 1-(or4)-(di-n-decylaminomethyl) triazole, 1-(or 4)-(di-n-dodecylaminomethyl)triazole, 1-(or 4)-(di-n-octadecylaminomethyl) triazole, 1-(or4)-(di-n-eicosylaminomethyl) triazole, 1-(or4)-[di-(prop-2′-enyl)aminomethyl] triazole, 1-(or4)-[di-(but-2′-enyl)aminomethyl] triazole, 1-(or4)-[di-(eicos-2′-enyl)aminomethyl] triazole, 1-(or4)-(di-cyclohexylaminomethyl) triazole, 1-(or 4)-(di-benzylaminomethyl)triazole, 1-(or 4)-(di-phenylaminomethyl) triazole, 1-(or4)-(4′-morpholinomethyl) triazole, 1-(or 4)-(1′-pyrrolidinomethyl)triazole, 1-(or 4)-(1′-piperidinomethyl) triazole, 1-(or4)-(1′-perhydoroazepinomethyl) triazole, 1-(or4)-(2′,2″-dihydroxyethyl)aminomethyl] triazole, 1-(or4)-(dibutoxypropyl-aminomethyl) triazole, 1-(or4)-(dibutylthiopropyl-aminomethyl) triazole, 1-(or4)-(di-butylaminopropyl-aminomethyl) triazole,1-(or-4)-(1-methanomine)-N,N-bis(2-ethylhexyl)-methyl benzotriazole,N,N-bis-(1- or 4-triazolylmethyl) laurylamine, N,N-bis-(1- or4-triazolylmethyl) oleylamine, N,N-bis-(1- or 4-triazolylmethyl)ethanolamine and N,N,N′,N′-tetra(1- or 4-triazolylmethyl) ethylenediamine.

The metal deactivating agents which can be used in the composition ofthe present disclosure includes, for example, benzotriazole and the4-alkylbenzotriazoles such as 4-methylbenzotriazole and4-ethylbenzotriazole; 5-alkylbenzotriazoles such as5-methylbenzotriazole, 5-ethylbenzotriazole; 1-alkylbenzotriazoles suchas 1-dioctylauainomethyl-2,3-benzotriazole; benzotriazole derivativessuch as the 1-alkyltolutriazoles, for example,1-dioctylaminomethyl-2,3-t-olutriazole; benzimidazole and benzimidazolederivatives such as 2-(alkyldithio)-benzimidazoles, for example, such as2-(octyldithio)-benzimidazole, 2-(decyldithio)benzimidazole and2-(dodecyldithio)-benzimidazole; 2-(alkyldithio)-toluimidazoles such as2-(octyldithio)-toluimidazole, 2-(decyldithio)-toluimidazole and2-(dodecyldithio)-toluimidazole; indazole and indazole derivatives oftoluimidazoles such as 4-alkylindazole, 5-alkylindazole; benzothiazole,2-mercaptobenzothiazole derivatives (manufactured by the Chiyoda KagakuCo. under the trade designation “Thiolite B-3100”) and2-(alkyldithio)benzothiazoles such as 2-(hexyldithio)benzothiazole and2-(octyldithio)benzothiazole; 2-(alkyl-dithio)toluthiazoles such as2-(benzyldithio)toluthiazole and 2-(octyldithio)toluthiazole,2-(N,N-dialkyldithiocarbamyl)benzothiazoles such as2-(N,N-diethyldithiocarbamyl)benzothiazole,2-(N,N-dibutyldithiocarbamyl)-benzotriazole and2-N,N-dihexyl-dithiocarbamyl)benzotriazole; benzothiazole derivatives of2-(N,N-dialkyldithiocarbamyl)toluthiazoles such as2-(N,N-diethyldithiocarbamyl)toluthiazole,2-(N,N-dibutyldithiocarbamyl)toluthiazole,2-(N,N-dihexyl-dithiocarbamyl)-toluthiazole; 2-(alkyldithio)benzoxazolessuch as 2-(octyldithio)benzoxazole, 2-(decyldithio)-benzoxazole and2-(dodecyldithio)benzoxazole; benzoxazole derivatives of2-(alkyldithio)toluoxazoles such as 2-(octyldithio)toluoxazole,2-(decyldithio)toluoxazole, 2-(dodecyldithio)toluoxazole;2,5-bis(alkyldithio)-1,3,4-thiadiazoles such as2,5-bis(heptyldithio)-1,3,4-thiadiazole,2,5-bis-(nonyldithio)-1,-3,4-thiadiazole,2,5-bis(dodecyldithio)-1,3,4-thiadiazole and2,5-bis-(octadecyldithio)-1,3,4-thiadiazole;2,5-bis(N,N-dialkyl-dithioca-rbamyl)-1,3,4-thiadiazoles such as2,5-bis(N,N-diethyldithiocarbamyl)-1,3,-4-thiadiazole,2,5-bis(N,N-dibutyldithiocarbamyl)-1,3,4-thiadiazole and2,5-bis(N,N-dioctyldithiocarbamyl) 1,3,4-thiadiazole; thiadiazolederivatives of 2-N,N-dialkyldithiocarbamyl-5-mercapto-1,3,4-thiadiazolessuch as 2-N,N-dibutyldithiocarbamyl-5-mercapto-1,3,4-thiadiazole and2-N,N-dioctyl-dithiocarbamyl-5-mercapto-1,3,4-thiadiazole, and triazolederivatives of 1-alkyl-2,4-triazoles such as1-dioctylaminomethyl-2,4-triazole; or concentrates and/or mixturesthereof.

Although their presence is not required to obtain the benefit of thepresent disclosure, the metal deactivator(s) and corrosion inhibitor(s)may be present from zero to about 1% by weight (e.g. from 0.01% to about0.5% by weight) of the total composition of the present disclosure.

Antiwear Additive(s) or Inhibitor(s)

In any aspect or embodiment described herein, the composition of thepresent disclosure comprises at least one (e.g., 1, 2, 3, 4, 5, or 6, ormore) antiwear additive or wear inhibitor. Any antiwear additive that isknown or that becomes known may be utilized in the lubricating of thepresent disclosure. The antiwear additive may be analkyldithiophosphate(s), aryl phosphate(s) and/or phosphite(s). Theantiwear additive(s) may be essentially free of metals, or they maycontain metal salts.

In certain embodiments, the antiwear additive is a phosphate ester orsalt thereof. A phosphate ester or salt may be a monohydrocarbyl,dihydrocarbyl or a trihydrocarbyl phosphate, wherein each hydrocarbylgroup is saturated. In an embodiment, each hydrocarbyl groupindependently contains from about 8 to about 30, or from about 12 up toabout 28, or from about 14 up to about 24, or from about 14 up to about18 carbons atoms. In an embodiment, the hydrocarbyl groups are alkylgroups. Examples of hydrocarbyl groups include at least one of tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl groups, andmixtures thereof.

A phosphate ester or salt is a phosphorus acid ester prepared byreacting at least one (e.g., 1, 2, 3, 4, or more) phosphorus acid oranhydride with a saturated alcohol. The phosphorus acid or anhydride cambe an inorganic phosphorus reagent, such as phosphorus pentoxide,phosphorus trioxide, phosphorus tetroxide, phosphorous acid, phosphoricacid, phosphorus halide, lower phosphorus esters, or a phosphorussulfide, including phosphorus pentasulfide, and the like. Lowerphosphorus acid esters may contain from 1 to about 7 carbon atoms ineach ester group. Alcohols used to prepare the phosphorus acid esters orsalts. Examples of commercially available alcohols and alcohol mixturesinclude Alfol 1218 (a mixture of synthetic, primary, straight-chainalcohols containing 12 to 18 carbon atoms); Alfol 20+ alcohols (mixturesof C18-C28 primary alcohols having mostly C20 alcohols as determined byGLC (gas-liquid-chromatography)); and Alfol22+ alcohols (C18-C28 primaryalcohols containing primarily C22 alcohols). Alfol alcohols areavailable from, e.g., Continental Oil Company. Another example of acommercially available alcohol mixture is Adol 60 (about 75% by weightof a straight chain C22 primary alcohol, about 15% of a C20 primaryalcohol, and about 8% of C18 and C24 alcohols). The Adol alcohols aremarketed by Ashland Chemical.

The antiwear additive may include at least one (e.g., a mixture of)monohydric fatty alcohol. For example, a mixture of monohydric fattyalcohols derived from naturally occurring triglycerides and ranging inchain length from C8 to C18 may be utilized as an antiwear additive. Avariety of monohydric fatty alcohol mixtures are available from Procter& Gamble Company. These mixtures contain various amounts of fattyalcohols containing 12, 14, 16, or 18 carbon atoms. For example, CO-1214is a fatty alcohol mixture containing 0.5% of C10 alcohol, 66.0% of C12alcohol, 26.0% of C14 alcohol and 6.5% of C16 alcohol.

Another group of commercially available alcohol mixtures include the“Neodol” products available from Shell Chemical Co. For example, Neodol23 is a mixture of C12 and C13 alcohols; Neodol 25 is a mixture of C12to C15 alcohols; and Neodol 45 is a mixture of C14 to C15 linearalcohols. The phosphate contains from about 14 to about 18 carbon atomsin each hydrocarbyl group. The hydrocarbyl groups of the phosphate maybe derived from a mixture of fatty alcohols having from about 14 up toabout 18 carbon atoms. The hydrocarbyl phosphate may also be derivedfrom a fatty vicinal diol. Fatty vicinal diols include, but not limitedto, those available from Ashland Oil under the general trade designationAdol 114 and Adol 158. The former is derived from a straight chain alphaolefin fraction of C11-C14, and the latter is derived from a C15-C18fraction.

Phosphate salts may be prepared by reacting an acidic phosphate esterwith an amine compound or a metallic base to form an amine or a metalsalt. The amines may be monoamines or polyamines. Useful amines includethose amines disclosed in U.S. Pat. No. 4,234,435.

Illustrative monoamines may contain a hydrocarbyl group, which containsfrom 1 to about 30 carbon atoms, or from 1 to about 12, or from 1 toabout 6. Examples of primary monoamines useful in the present disclosureinclude methylamine, ethylamine, propylamine, butylamine,cyclopentylamine, cyclohexylamine, octylamine, dodecylamine, allylamine,cocoamine, stearylamine, and laurylamine. Examples of secondarymonoamines include dimethylamine, diethylamine, dipropylamine,dibutylamine, dicyclopentylamine, dicyclohexylamine, methylbutylamine,ethylhexylamine, etc.

An amine may be a fatty (C8-C30) amine which includes n-octylamine,n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine,n-octadecylamine, oleyamine, etc. Also useful fatty amines includecommercially available fatty amines, such as “Armeen” amines (productsavailable from Akzo Chemicals, Chicago, Ill.), e.g. Armeen C, Armeen O,Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein theletter designation relates to the fatty group, such as coco, oleyl,tallow, or stearyl groups.

Other useful amines include primary ether amines, such as thoserepresented by the formula:

R″(OR′)xNH2,

wherein: R′ is a divalent alkylene group having about 2 to about 6carbon atoms; x is a number from one to about 150, or from about one toabout five, or one; and R″ is a hydrocarbyl group of about 5 to about150 carbon atoms.

An exemplary or illustrative ether amine is available under the nameSURFAM® amines produced and marketed by Mars Chemical Company, Atlanta,Ga. Additional exemplary ether amines include those identified as SURFAMP14B (decyloxypropylamine), SURFAM P16A (linear C16), and SURFAM P17B(tridecyloxypropylamine). The carbon chain lengths (i.e., C14, etc.) ofthe SURFAM ether amines described above and used hereinafter areapproximate and include the oxygen ether linkage.

A further illustrative amine is a tertiary-aliphatic primary amine. Forexample, the aliphatic group, such as an alkyl group, contains fromabout 4 to about 30, or from about 6 to about 24, or from about 8 toabout 22 carbon atoms. Usually the tertiary alkyl primary amines aremonoamines the alkyl group is a hydrocarbyl group containing from one toabout 27 carbon atoms. Such amines are illustrated by tert-butylamine,tert-hexylamine, 1-methyl-1-amino-cyclohexane, tert-octylamine,tert-decylamine, tert-dodecylamine, tert-tetradecylamine,tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine,tert-octacosanylamine, and combinations thereof. Mixtures of tertiaryaliphatic amines may also be used in preparing the phosphate salt.Illustrative of amine mixtures of this type are “Primene 81R”, which isa mixture of C11-C14 tertiary alkyl primary amines, and “Primene JMT”,which is a similar mixture of C18-C22 tertiary alkyl primary amines(both are available from Rohm and Haas Company). The tertiary aliphaticprimary amines and methods for their preparation are known to those ofordinary skill in the art.

Another illustrative amine is a heterocyclic polyamine. The heterocyclicpolyamines include aziridines, azetidines, azolidines, tetra- anddihydropyridines, pyrroles, indoles, piperidines, imidazoles, di- andtetra-hydroimidazoles, piperazines, isoindoles, purines, morpholines,thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines,N-aminoalkyl-piperazines, N,N′-diaminoalkylpiperazines, azepines,azocines, azonines, azecines and tetra-, di- and perhydro derivatives ofeach of the above, and mixtures of two or more (e.g., 2, 3, 4, 5, 6, ormore) of these heterocyclic amines. In certain embodiments, theheterocyclic amines are saturated 5- and 6-membered heterocyclic aminescontaining only nitrogen, oxygen and/or sulfur in the hetero ring,especially the piperidines, piperazines, thiomorpholines, morpholines,pyrrolidines, and the like. Piperidine, aminoalkyl substitutedpiperidines, piperazine, aminoalkyl substituted piperazines, morpholine,aminoalkyl substituted morpholines, pyrrolidine, andaminoalkyl-substituted pyrrolidines, are especially preferred. Usuallythe aminoalkyl substituents are substituted on a nitrogen atom formingpart of the hetero ring. Specific examples of such heterocyclic aminesinclude N-aminopropylmorpholine, N-aminoethylpiperazine, andN,N′-diaminoethylpiperazine. Hydroxy heterocyclic polyamines are alsouseful. Examples include N-(2-hydroxyethyl)cyclohexylamine,3-hydroxycyclopentylamine, parahydroxyaniline, N-hydroxyethylpiperazine,and the like.

The metal salts of the phosphorus acid esters may be prepared by thereaction of a metal base with the acidic phosphorus ester. The metalbase may be any metal compound capable of forming a metal salt. Examplesof metal bases include metal oxides, hydroxides, carbonates, sulfates,borates, or the like. The metals of the metal base include Group IA,IIA, IB through VIIB, and VIII metals (CAS version of the Periodic Tableof the Elements). These metals include the alkali metals, alkaline earthmetals and transition metals. In an embodiment, the metal is a Group IIAmetal, such as calcium or magnesium, Group IIB metal, such as zinc, or aGroup VIIB metal, such as manganese. In particular embodiments, themetal is magnesium, calcium, manganese or zinc. Examples of metalcompounds which may be reacted with the phosphorus acid include zinchydroxide, zinc oxide, copper hydroxide, copper oxide, etc.

The composition of the present disclosure also may include a fattyimidazoline or a reaction product of a fatty carboxylic acid and atleast one polyamine. The fatty imidazoline has fatty substituentscontaining from 8 to about 30, or from about 12 to about 24 carbonatoms. The substituent may be saturated or unsaturated, for example,heptadeceneyl derived olyel groups. In a particular embodiment, thesubstituents are saturated. In one aspect, the fatty imidazoline may beprepared by reacting a fatty carboxylic acid with apolyalkylenepolyamine. The fatty carboxylic acids are can be mixtures ofstraight and branched chain fatty carboxylic acids containing about 8 toabout 30 carbon atoms, or from about 12 to about 24, or from about 16 toabout 18. Carboxylic acids include the polycarboxylic acids orcarboxylic acids or anhydrides having from 2 to about 4 carbonyl groups,(e.g. 2 carbonyl groups). The polycarboxylic acids include succinicacids and anhydrides and Diels-Alder reaction products of unsaturatedmonocarboxylic acids with unsaturated carboxylic acids (such as acrylic,methacrylic, maleic, fumaric, crotonic and itaconic acids). Inparticular embodiments, the fatty carboxylic acids are fattymonocarboxylic acids, having from about 8 to about 30, (e.g. about 12 toabout 24 carbon atoms), such as octanoic, oleic, stearic, linoleic,dodecanoic, and tall oil acids. In an embodiment, the fatty carboxylicacid is stearic acid. The fatty carboxylic acid or acids are reactedwith at least one polyamine. The polyamines may be aliphatic,cycloaliphatic, heterocyclic or aromatic. Examples of the polyaminesinclude alkylene polyamines and heterocyclic polyamines.

The antiwear additive according to the present disclosure has very higheffectiveness when used in low concentrations and is free of chlorine.For the neutralization of the phosphoric esters, the latter are takenand the corresponding amine slowly added with stirring. The resultingheat of neutralization is removed by cooling. The antiwear additiveaccording to the present disclosure can be incorporated into therespective base liquid with the aid of fatty substances (e.g., tall oilfatty acid, oleic acid, etc.) as solubilizers. The base liquids used arenapthenic or paraffinic base oils, synthetic oils (e.g., polyglycols,mixed polyglycols), polyolefins, carboxylic esters, etc.

In further embodiments, the compositions of the present disclosure cancontain at least one phosphorus containing antiwear additive. Examplesof such additives are amine phosphate antiwear additives such as thatknown under the trade name IRGALUBE 349 and/or triphenylphosphorothionate antiwear additives, such as that known under the tradename IRGALUBE TPPT. Such amine phosphates may be present in an amount offrom about 0.01 to about 2% (e.g. about 0.2 to about 1.5%) by weight ofthe lubricant composition, while such phosphorothionates are suitablypresent in an amount of from about 0.01 to about 3% (e.g., about 0.5 toabout 1.5%) by weight of the composition of the present disclosure. Amixture of an amine phosphate and phosphorothionate may be employed.

Neutral organic phosphates may be present in an amount from zero toabout 4% (e.g., about 0.1 to about 2.5%) by weight of the composition ofthe present disclosure. The above amine phosphates can be mixed togetherto form a single component capable of delivering antiwear performance.The neutral organic phosphate is also a conventional ingredient oflubricating oils.

Phosphates for use in the present disclosure include phosphates, acidphosphates, phosphites, and acid phosphites. The phosphates includetriaryl phosphates, trialkyl phosphates, trialkylaryl phosphates,triarylalkyl phosphates, trialkenyl phosphates, or combinations thereof.As specific examples of these, referred to are triphenyl phosphate,tricresyl phosphate, benzyldiphenyl phosphate, ethyldiphenyl phosphate,tributyl phosphate, ethyldibutyl phosphate, cresyldiphenyl phosphate,dicresylphenyl phosphate, ethylphenyldiphenyl phosphate,diethylphenylphenyl phosphate, propylphenyldiphenyl phosphate,dipropylphenylphenyl phosphate, triethylphenyl phosphate,tripropylphenyl phosphate, butylphenyldiphenyl phosphate,dibutylphenylphenyl phosphate, tributylphenyl phosphate, trihexylphosphate, tri(2-ethylhexyl) phosphate, tridecyl phosphate, trilaurylphosphate, trimyristyl phosphate, tripalmityl phosphate, tristearylphosphate, trioleyl phosphate, or combinations thereof.

The acid phosphates include, for example, 2-ethylhexyl acid phosphate,ethyl acid phosphate, butyl acid phosphate, oleyl acid phosphate,tetracosyl acid phosphate, isodecyl acid phosphate, lauryl acidphosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearylacid phosphate, or combinations thereof.

The phosphites include, for example, triethyl phosphite, tributylphosphite, triphenyl phosphite, tricresyl phosphite, tri(nonylphenyl)phosphite, tri(2-ethylhexyl) phosphite, tridecyl phosphite, trilaurylphosphite, triisooctyl phosphite, diphenylisodecyl phosphite, tristearylphosphite, trioleyl phosphite, or combinations thereof.

The acid phosphites include, for example, dibutyl hydrogenphosphite,dilauryl hydrogenphosphite, dioleyl hydrogenphosphite, distearylhydrogenphosphite, diphenyl hydrogenphosphite, or combinations thereof.

Amines that form amine salts with such phosphates include, for example,mono-substituted amines, di-substituted amines and tri-substitutedamines. Examples of the mono-substituted amines include butylamine,pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine,stearylamine, oleylamine and benzylamine; and those of thedi-substituted amines include dibutylamine, dipentylamine, dihexylamine,dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine,dioleylamine, dibenzylamine, stearyl monoethanolamine, decylmonoethanolamine, hexyl monopropanolamine, benzyl monoethanolamine,phenyl monoethanolamine, and tolyl monopropanolamine. Examples oftri-substituted amines include tributylamine, tripentylamine,trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine,tristearylamine, trioleylamine, tribenzylamine, dioleylmonoethanolamine, dilauryl monopropanolamine, dioctyl monoethanolamine,dihexyl monopropanolamine, dibutyl monopropanolamine, oleyldiethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyldipropanolamine, butyl diethanolamine, benzyl diethanolamine, phenyldiethanolamine, tolyl dipropanolamine, xylyl diethanolamine,triethanolamine, and tripropanolamine. Phosphates or their amine saltsare added to the base oil in an amount from zero to about 5% by weight,(e.g. from about 0.1 to about 2% by weight) relative to the total weightof the composition of the present disclosure.

Illustrative carboxylic acids to be reacted with amines include, forexample, aliphatic carboxylic acids, dicarboxylic acids (dibasic acids),aromatic carboxylic acids, or combinations thereof. The aliphaticcarboxylic acids have from 8 to 30 carbon atoms, and may be saturated orunsaturated, and linear or branched. Specific examples of the aliphaticcarboxylic acids include pelargonic acid, lauric acid, tridecanoic acid,myristic acid, palmitic acid, stearic acid, isostearic acid, eicosanoicacid, behenic acid, triacontanoic acid, caproleic acid, undecylenicacid, oleic acid, linolenic acid, erucic acid, linoleic acid, orcombinations thereof. Specific examples of the dicarboxylic acidsinclude octadecylsuccinic acid, octadecenylsuccinic acid, adipic acid,azelaic acid, sebacic acid, or combinations thereof. One example of thearomatic carboxylic acids is salicylic acid. Illustrative amines to bereacted with carboxylic acids include, for example,polyalkylene-polyamines, such as diethylenetriamine,triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,hexaethyleneheptamine, heptaethyleneoctamine, dipropylenetriamine,tetrapropylenepentamine, hexabutyleneheptamine, or combinations thereof;and alkanolamines, such as monoethanolamine and diethanolamine. Ofthese, preferred are a combination of isostearic acid,tetraethylenepentamine, or combinations thereof; and a combination ofoleic acid and diethanolamine. Reaction products of carboxylic acids andamines may be added to the base oil in an amount of from zero to about5% by weight (e.g. from about 0.03 to about 3% by weight) relative tothe total weight of the composition of the present disclosure.

Other illustrative antiwear additives include phosphites,thiophosphites, phosphates, and thiophosphates, including mixedmaterials having, for instance, one or two sulfur atoms, i.e., monothio-or dithio compounds. As used herein, the term “hydrocarbyl substituent”or “hydrocarbyl group” is used in its ordinary sense, which iswell-known to those skilled in the art. Specifically, it refers to agroup primarily composed of carbon and hydrogen atoms and is attached tothe remainder of the molecule through a carbon atom and does not excludethe presence of other atoms or groups in a proportion insufficient todetract from the molecule having a predominantly hydrocarbon character.In general, no more than two, preferably no more than one,non-hydrocarbon substituent will be present for every ten carbon atomsin the hydrocarbyl group; typically, there will be no non-hydrocarbonsubstituents in the hydrocarbyl group. A more detailed definition of theterms “hydrocarbyl substituent” or “hydrocarbyl group,” is described inU.S. Pat. No. 6,583,092.

Specific examples of some phosphites and thiophosphites within the scopeof the disclosure include phosphorous acid, mono-, di- ortri-thiophosphorous acid, mono-, di- or tri-propyl phosphite or mono-,di- or tri-thiophosphite; mono-, di- or tri-butyl phosphite or mono-,di- or tri-thiophosphite; mono-, di- or tri-amyl phosphite or mono-, di-or tri-thiophosphite; mono-, di- or tri-hexyl phosphite; or mono-, di-or tri-thiophosphite; mono-, di- or tri-phenyl phosphite; or mono-, di-or tri-thiophosphite; mono-, di- or tri-tolyl phosphite; or mono-, di-or tri-thiophosphite; mono-, di- or tri-cresyl phosphite; or mono-, di-or tri-thiophosphite; dibutyl phenyl phosphite; or mono-, di- ortri-phosphite; amyl dicresyl phosphite; or mono-, di- ortri-thiophosphite, and any of the above with substituted groups, such aschlorophenyl or chlorobutyl.

Specific examples of the phosphates and thiophosphates within the scopeof the disclosure include phosphoric acid, mono-, di-, ortri-thiophosphoric acid, mono-, di-, or tri-propyl phosphate or mono-,di-, or tri-thiophosphate; mono-, di-, or tri-butyl phosphate or mono-,di-, or tri-thiophosphate; mono-, di-, or tri-amyl phosphate or mono-,di-, or tri-thiophosphate; mono-, di-, or tri-hexyl phosphate or mono-,di-, or tri-thiophosphate; mono-, di-, or tri-phenyl phosphate or mono-,di-, or tri-thiophosphate; mono-, di-, or tritolyl phosphate or mono-,di-, or trithiophosphate; mono-, di-, or tri-cresyl phosphate or mono-,di-, or tri-thiophosphate; dibutyl phenyl phosphate or mono-, di-, ortri-phosphate, amyl dicresyl phosphate or mono-, di-, ortri-thiophosphate, and any of the above with substituted groups, such aschlorophenyl or chlorobutyl.

These phosphorus compounds may be prepared by well-known reactions. Forexample, the reaction of an alcohol or a phenol with phosphorustrichloride or by a transesterification reaction. Alcohols and phenolscan be reacted with phosphorus pentoxide to provide a mixture of analkyl or aryl phosphoric acid and a dialkyl or diaryl phosphoric acid.Alkyl phosphates can also be prepared by the oxidation of thecorresponding phosphites. Thiophosphates can be prepared by the reactionof phosphites with elemental sulfur. In any case, the reaction can beconducted with moderate heating. Moreover, various phosphorus esters canbe prepared by reaction using other phosphorus esters as startingmaterials. Thus, medium chain (C9 to C22) phosphorus esters have beenprepared by reaction of dimethylphosphite with a mixture of medium-chainalcohols by means of a thermal transesterification or an acid- orbase-catalyzed transesterification. See, for example, U.S. Pat. No.4,752,416. Most such materials are also commercially available; forinstance, triphenyl phosphite is available from Albright and Wilson asDuraphos TPP™; di-n-butyl hydrogen phosphite from Albright and Wilson asDuraphos DBHP™; and triphenylthiophosphate from Ciba Specialty Chemicalsas Irgalube TPPT™.

Examples of esters of the dialkylphosphorodithioic acids include estersobtained by reaction of the dialkyl phosphorodithioic acid with analpha, beta-unsaturated carboxylic acid (e.g., methyl acrylate) and,optionally an alkylene oxide such as propylene oxide.

One or more of the above-identified metal dithiophosphates may be usedfrom about zero to about 2% by weight (e.g., from about 0.1 to about 1%by weight) based on the weight of the total composition.

The hydrocarbyl in the dithiophosphate may be alkyl, cycloalkyl, aralkylor alkaryl groups, or a substantially hydrocarbon group of similarstructure. Illustrative alkyl groups include isopropyl, isobutyl,n-butyl, sec-butyl, the various amyl groups, n-hexyl, methylisobutyl,heptyl, 2-ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl, decyl,dodecyl, tridecyl, etc. Illustrative lower alkylphenyl groups includebutylphenyl, amylphenyl, heptylphenyl, etc. Cycloalkyl groups likewiseare useful and these include chiefly cyclohexyl and the loweralkyl-cyclohexyl radicals. Many substituted hydrocarbon groups may alsobe used, e.g., chloropentyl, dichlorophenyl, and dichlorodecyl.

The phosphorodithioic acids from which the metal salts useful in thisdisclosure are prepared are well known. Examples ofdihydrocarbylphosphorodithioic acids and metal salts, and processes forpreparing such acids and salts are found in, for example U.S. Pat. Nos.4,263,150; 4,289,635; 4,308,154; and 4,417,990. These patents are herebyincorporated by reference.

The phosphorodithioic acids may be prepared by the reaction of aphosphorus sulfide with an alcohol or phenol or mixtures of alcohols. Anexemplary reaction involves four moles of the alcohol or phenol and onemole of phosphorus pentasulfide, and may be carried out within thetemperature range from about 50° C. to about 200° C. Thus, thepreparation of O,O-di-n-hexyl phosphorodithioic acid involves thereaction of a mole of phosphorus pentasulfide with four moles of n-hexylalcohol at about 100° C. for about two hours. Hydrogen sulfide isliberated and the residue is the desired acid. The preparation of themetal salts of these acids may be effected by reaction with metalcompounds as well known in the art.

The metal salts of dihydrocarbyldithiophosphates, which are useful inthe present disclosure, include those salts containing Group I metals,Group II metals, aluminum, lead, tin, molybdenum, manganese, cobalt, andnickel. The Group II metals, aluminum, tin, iron, cobalt, lead,molybdenum, manganese, nickel and copper are among the preferred metals.Zinc and copper are especially useful metals. Examples of metalcompounds which may be reacted with the acid include lithium oxide,lithium hydroxide, sodium hydroxide, sodium carbonate, potassiumhydroxide, potassium carbonate, silver oxide, magnesium oxide, magnesiumhydroxide, calcium oxide, zinc hydroxide, strontium hydroxide, cadmiumoxide, cadmium hydroxide, barium oxide, aluminum oxide, iron carbonate,copper hydroxide, lead hydroxide, tin butylate, cobalt hydroxide, nickelhydroxide, nickel carbonate, and the like.

In some instances, the incorporation of certain ingredients such assmall amounts of the metal acetate or acetic acid in conjunction withthe metal reactant will facilitate the reaction and result in animproved product. For example, the use of up to about 5% of zinc acetatein combination with the required amount of zinc oxide facilitates theformation of a zinc phosphorodithioate with potentially improvedperformance properties.

Especially useful metal phosphorodithloates can be prepared fromphosphorodithloic acids, which in turn are prepared by the reaction ofphosphorus pentasulfide with mixtures of alcohols. In addition, the useof such mixtures enables the utilization of less expensive alcohols,which individually may not yield oil-soluble phosphorodithioic acids.Thus, a mixture of isopropyl and hexylalcohols can be used to produce avery effective, oil-soluble metal phosphorodithioate. For the samereason mixtures of phosphorodithioic acids can be reacted with the metalcompounds to form less expensive, oil-soluble salts.

The mixtures of alcohols may be mixtures of different primary alcohols,mixtures of different secondary alcohols, or mixtures of primary andsecondary alcohols. Examples of useful mixtures include: n-butanol andn-octanol; n-pentanol and 2-ethyl-1-hexanol; isobutanol and n-hexanol;isobutanol and isoamyl alcohol; isopropanol and 2-methyl-4-pentanol;isopropanol and sec-butyl alcohol; isopropanol and isooctyl alcohol; andthe like.

Organic triesters of phosphorus acids are also employed in lubricants.Exemplary esters include triarylphosphates, trialkyl phosphates, neutralalkylaryl phosphates, alkoxyalkyl phosphates, triaryl phosphite,trialkylphosphite, neutral alkyl aryl phosphites, neutral phosphonateesters and neutral phosphine oxide esters. In one embodiment, the longchain dialkyl phosphonate esters are used. For example, the dimethyl-,diethyl-, and/or dipropyl-oleyl phohphonates can be used. Neutral acidsof phosphorus acids are the triesters rather than an acid (HO—P) or asalt of an acid.

Any C4 to C8 alkyl or higher phosphate ester may be employed in thedisclosure. For example, tributyl phosphate (TBP) and tri isooctalphosphate (TOF) can be used. The specific triphosphate ester orcombination of esters can easily be selected by one skilled in the artto adjust the density, viscosity, etc., of the formulated fluid. Mixedesters, such as dibutyl octyl phosphate or the like may be employedrather than a mixture of two or more trialkyl phosphates.

A trialkyl phosphate is often useful to adjust the specific gravity ofthe formulation, but it is desirable that the specific trialkylphosphate be a liquid at low temperatures. Consequently, a mixed estercontaining at least one partially alkylated with a C3 to C4 alkyl groupis very desirable, for example, 4-isopropylphenyl diphenyl phosphate or3-butylphenyl diphenyl phosphate. Even more desirable is a triarylphosphate produced by partially alkylating phenol with butylene orpropylene to form a mixed phenol which is then reacted with phosphorusoxychloride as taught in U.S. Pat. No. 3,576,923.

Any mixed triaryl phosphate (TAP) esters may be used as cresyl diphenylphosphate, tricresyl phosphate, mixed xylyl cresyl phosphates, loweralkylphenyl/phenyl phosphates, such as mixed isopropylphenyl/phenylphosphates, t-butylphenyl phenyl phosphates. These esters are usedextensively as plasticizers, functional fluids, gasoline additives,flame-retardant additives and the like.

A metal alkylthiophosphate and more particularly a metal dialkyl dithiophosphate in which the metal constituent is zinc, or zinc dialkyl dithiophosphate (ZDDP) can be a useful component of the lubricating oils ofthis disclosure. ZDDP can be derived from primary alcohols, secondaryalcohols or mixtures thereof. ZDDP compounds are of the formula:

Zn[SP(S)(OR1)(OR2)]₂

wherein R1 and R2 are C1-C18 alkyl groups (e.g. C2-C12 alkyl groups).

These alkyl groups may be straight chain or branched. Alcohols used inthe ZDDP can be propanol, 2-propanol, butanol, secondary butanol,pentanols, hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol,2-ethyl hexanol, alkylated phenols, and the like. Mixtures of secondaryalcohols or of primary and secondary alcohol can be utilized. Alkyl arylgroups may also be used.

Exemplary zinc dithiophosphates that are commercially available includesecondary zinc dithiophosphates, such as those available from forexample, The Lubrizol Corporation under the trade designations “LZ677A”, “LZ 1095” and “LZ 1371”, from for example Chevron Oronite underthe trade designation “OLOA 262”, and from for example Afton Chemicalunder the trade designation “HITEC 7169”.

ZDDP may be used in amounts of from about zero to about 3 weight percent(e.g. from about 0.05 weight percent to about 2 weight percent, fromabout 0.1 weight percent to about 1.5 weight percent, or from about 0.1weight percent to about 1 weight percent) based on the total weight ofthe composition fo the present disclosure, although more or less canoften be used advantageously. A secondary ZDDP may be present in anamount of from zero to about 1 weight percent of the total weight of thecomposition of the present disclosure.

Still other illustrative antiwear additives useful in this disclosureinclude, for example, molybdenum disulfide, calcium carbonate, graphite,dicalcium carbonate, and the like. Such materials are commerciallyavailable in a range of sizes and crystalline structures.

Extreme Pressure Agent(s)

In any aspect or embodiment described herein, the composition of thepresent disclosure comprises at least one (e.g., 1, 2, 3, or 4, or more)extreme pressure agent. Any extreme pressure agent that is known or thatbecomes know may be utilized in the composition of the presentdisclosure.

The extreme pressure agents can be at least one sulfur-based extremepressure agents, such as sulfides, sulfoxides, sulfones,thiophosphinates, thiocarbonates, sulfurized fats and oils, sulfurizedolefins, the like, or combinations thereof; at least onephosphorus-based extreme pressure agents, such as phosphoric acid esters(e.g., tricresyl phosphate (TCP) and the like), phosphorous acid esters,phosphoric acid ester amine salts, phosphorous acid ester amine salts,the like, or combinations thereof; halogen-based extreme pressureagents, such as chlorinated hydrocarbons, the like, or combinationsthereof; organometallic extreme pressure agents, such as thiophosphoricacid salts (e.g., zinc dithiophosphate (ZnDTP) and the like),thiocarbamic acid salts, or combinations thereof; and the like.

The phosphoric acid ester, thiophosphoric acid ester, and amine saltsthereof functions to enhance the lubricating performances, and can beselected from known compounds conventionally employed as extremepressure agents. For example, phosphoric acid esters, a thiophosphoricacid ester, or an amine salt thereof which has an alkyl group, analkenyl group, an alkylaryl group, or an aralkyl group, any of whichcontains approximately 3 to 30 carbon atoms, may be employed.

Examples of the phosphoric acid esters include aliphatic phosphoric acidesters such as triisopropyl phosphate, tributyl phosphate, ethyl dibutylphosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, trilaurylphosphate, tristearyl phosphate, and trioleyl phosphate; and aromaticphosphoric acid esters such as benzyl phenyl phosphate, allyl diphenylphosphate, triphenyl phosphate, tricresyl phosphate, ethyl diphenylphosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate,ethylphenyl diphenyl phosphate, diethylphenyl phenyl phosphate,propylphenyl diphenyl phosphate, dipropylphenyl phenyl phosphate,triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyldiphenyl phosphate, dibutylphenyl phenyl phosphate, and tributylphenylphosphate. In an embodiment, the phosphoric acid ester is atrialkylphenyl phosphate.

Examples of the thiophosphoric acid esters include aliphaticthiophosphoric acid esters such as triisopropyl thiophosphate, tributylthiophosphate, ethyl dibutyl thiophosphate, trihexyl thiophosphate,tri-2-ethylhexyl thiophosphate, trilauryl thiophosphate, tristearylthiophosphate, and trioleyl thiophosphate; and aromatic thiophosphoricacid esters such as benzyl phenyl thiophosphate, allyl diphenylthiophosphate, triphenyl thiophosphate, tricresyl thiophosphate, ethyldiphenyl thiophosphate, cresyl diphenyl thiophosphate, dicresyl phenylthiophosphate, ethylphenyl diphenyl thiophosphate, diethylphenyl phenylthiophosphate, propylphenyl diphenyl thiophosphate, dipropylphenylphenyl thiophosphate, triethylphenyl thiophosphate, tripropylphenylthiophosphate, butylphenyl diphenyl thiophosphate, dibutylphenyl phenylthiophosphate, and tributylphenyl thiophosphate. In an embodiment, thethiophosphoric acid ester is a trialkylphenyl thiophosphate.

Also employable are amine salts of the above-mentioned phosphates andthiophosphates. Amine salts of acidic alkyl or aryl esters of thephosphoric acid and thiophosphoric acid are also employable. In anembodiment, the amine salt is an amine salt of trialkylphenyl phosphateor an amine salt of alkyl phosphate.

One or any combination of the compounds selected from the groupconsisting of a phosphoric acid ester, a thiophosphoric acid ester, andan amine salt thereof may be used.

The phosphorus acid ester and/or its amine salt function to enhance thelubricating performance of the composition, and can be selected fromknown compounds conventionally employed as extreme pressure agents. Forexample, the extreme pressure agent can be a phosphorus acid ester or anamine salt thereof, which has an alkyl group, an alkenyl group, analkylaryl group, or an aralkyl group, any of which containsapproximately 3 to 30 carbon atoms.

Examples of phosphorus acid esters that may be used includes aliphaticphosphorus acid esters, such as triisopropyl phosphite, tributylphosphite, ethyl dibutyl phosphite, trihexyl phosphite,tri-2-ethylhexylphosphite, trilauryl phosphite, tristearyl phosphite,and trioleyl phosphite; and aromatic phosphorus acid esters such asbenzyl phenyl phosphite, allyl diphenylphosphite, triphenyl phosphite,tricresyl phosphite, ethyl diphenyl phosphite, tributyl phosphite, ethyldibutyl phosphite, cresyl diphenyl phosphite, dicresyl phenyl phosphite,ethylphenyl diphenyl phosphite, diethylphenyl phenyl phosphite,propylphenyl diphenyl phosphite, dipropylphenyl phenyl phosphite,triethylphenyl phosphite, tripropylphenyl phosphite, butylphenyldiphenyl phosphite, dibutylphenyl phenyl phosphite, and tributylphenylphosphite. Also favorably employed are dilauryl phosphite, dioleylphosphite, dialkyl phosphites, and diphenyl phosphite. In certainembodiments, the phosphorus acid ester is a dialkyl phosphite or atrialkyl phosphite.

The phosphate salt may be derived from a polyamine, such as alkoxylateddiamines, fatty polyamine diamines, alkylenepolyamines, hydroxycontaining polyamines, condensed polyamines arylpolyamines, andheterocyclic polyamines. Examples of these amines include EthoduomeenT/13 and T/20, which are ethylene oxide condensation products ofN-tallowtrimethylenediamine containing 3 and 10 moles of ethylene oxideper mole of diamine, respectively.

In another embodiment, the polyamine is a fatty diamine. The fattydiamine may include mono- or dialkyl, symmetrical or asymmetricalethylene diamines, propane diamines (1,2 or 1,3), and polyamine analogsof the above. Suitable commercial fatty polyamines are Duomeen C(N-coco-1,3-diaminopropane), Duomeen S (N-soya-1,3-diaminopropane),Duomeen T (N-tallow-1,3-diaminopropane), and Duomeen O(N-oleyl-1,3-diaminopropane). “Duomeens” are commercially available fromArmak Chemical Co., Chicago, Ill.

Such alkylenepolyamines include methylenepolyamines, ethylenepolyamines,butylenepolyamines, propylenepolyamines, pentylenepolyamines, etc. Thehigher homologs and related heterocyclic amines, such as piperazines andN-amino alkyl-substituted piperazines, are also included. Specificexamples of such polyamines are ethylenediamine, triethylenetetramine,tris-(2-aminoethyl)amine, propylenediamine, trimethylenediamine,tripropylenetetramine, tetraethylenepentamine, hexaethyleneheptamine,pentaethylenehexamine, etc. Higher homologs obtained by condensing twoor more of the above-noted alkyleneamines are similarly useful as aremixtures of two or more of the aforedescribed polyamines.

In one embodiment the polyamine is an ethylenepolyamine. Such polyaminesare described in detail under the heading Ethylene Amines in KirkOthmer's “Encyclopedia of Chemical Technology”, 2nd Edition, Vol. 7,pages 22-37, Interscience Publishers, New York (1965).Ethylenepolyamines can be a complex mixture of polyalkylenepolyamines,including cyclic condensation products.

Other useful types of polyamine mixtures are those resulting fromstripping of the above-described polyamine mixtures to leave, asresidue, what is often termed “polyamine bottoms”. The alkylenepolyaminebottoms can be characterized as having less than 2%, usually less than1% (by weight) material boiling below about 200° C. An exemplary sampleof such ethylene polyamine bottoms obtained from the Dow ChemicalCompany of Freeport, Tex. designated “E-100”. These alkylenepolyaminebottoms include cyclic condensation products, such as piperazine, andhigher analogs of diethylenetriamine, triethylenetetramine and the like.These alkylenepolyamine bottoms can be reacted solely with the acylatingagent or they can be used with other amines, polyamines, or mixturesthereof. Another useful polyamine is a condensation reaction between atleast one hydroxy compound with at least one polyamine reactantcontaining at least one primary or secondary amino group. In anembodiment, the hydroxy compounds are alcohols and amines. Thepolyhydric alcohols are described below. In one embodiment, the hydroxycompounds are polyhydric amines. Polyhydric amines include any of theabove-described monoamines reacted with an alkylene oxide (e.g.,ethylene oxide, propylene oxide, butylene oxide, etc.) having from twoto about 20 carbon atoms, or from two to about four. Examples ofpolyhydric amines include tri-(hydroxypropyl)amine,tris-(hydroxymethyl)amino methane, 2-amino-2-methyl-1,3-propanediol,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, andN,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine. IN an embodiment, thepolyhydric amin is tris(hydroxymethyl)aminomethane (THAM).

Polyamines which react with the polyhydric alcohol or amine to form thecondensation products or condensed amines, are described above. In anembodiment, the polyamine includes at least one of triethylenetetramine(TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), andmixtures of polyamines, such as the above-described “amine bottoms”.

In some embodiments, the extreme pressure additive or additives includessulphur-based extreme pressure additives, such as dialkyl sulphides,dibenzyl sulphide, dialkyl polysulphides, dibenzyl disulphide, alkylmercaptans, dibenzothiophene, 2,2′-dithiobis(benzothiazole), orcombinations thereof; phosphorus-based extreme pressure additives, suchas trialkyl phosphates, triaryl phosphates, trialkyl phosphonates,trialkyl phosphites, triaryl phosphites, dialkylhydrozine phosphites, orcombinations thereof; and/or phosphorus- and sulphur-based extremepressure additives, such as zinc dialkyldithiophosphates,dialkylthiophosphoric acid, trialkyl thiophosphate esters, acidicthiophosphate esters, trialkyl trithiophosphates, or combinationsthereof. Extreme pressure additives can be used individually or in theform of mixtures, conveniently in an amount within the range from zeroto about 2% by weight of the composition of the present disclosure.

Still other illustrative extreme pressure additives useful in thisdisclosure include, for example, molybdenum disulfide, calciumcarbonate, graphite, dicalcium carbonate, and the like. Such materialsare commercially available in a range of sizes and crystallinestructures.

Dispersant(s)

In other embodiments, the composition of the present disclosurecomprises at least one (e.g., 1, 2, 3, or 4, or more) dispersant. Duringmachine operation, oil-insoluble oxidation byproducts are produced. Thedispersant may be added to help keep these byproducts in solution, thusdiminishing their deposition on metal surfaces. Any dispersant that isknown or that becomes know may be utilized in the composition of thepresent disclosure. The dispersant may be present in an amount of ≤about 1.5 wt. %, ≤ about 1.25 wt. %, or ≤ about 1 wt. %. For example,the dispersant may be present in an amount of about 0.1 to about 1.5 wt.%, about 0.1 to about 1.25 wt. %, about 0.1 to about 1 wt. %, about 0.1to about 0.5 wt. %, about 0.25 to about 1.5 wt. %, about 0.25 to about1.25 wt. %, about 0.5 to about 1 wt. %, about 0.5 to about 1.5 wt. %,about 0.5 to about 1.25 wt. %, about 0.5 to about 1 wt. %, about 0.75 toabout 1.5 wt. %, about 0.75 to about 1.25 wt. %, or about 1 to about 1.5wt. %.

In some embodiments, the dispersants are ashless or ash-forming innature. In an embodiment, the dispersant is an ashless. The so calledashless are organic materials that form substantially no ash uponcombustion. For example, non-metal-containing or borated metal-freedispersants are considered ashless. In contrast, metal-containingdetergents form ash upon combustion.

Suitable dispersants may contain a polar group attached to a relativelyhigh molecular weight hydrocarbon chain (e.g., about 50 to about 400carbon atoms). In certain embodiments, the polar group contains at leastone element of nitrogen, oxygen, or phosphorus.

A particularly useful class of dispersants are the (poly)alkenylsuccinicderivatives, which may be produced by the reaction of a long chainhydrocarbyl substituted succinic compound, e.g. a hydrocarbylsubstituted succinic anhydride, with a polyhydroxy or polyaminocompound. The long chain hydrocarbyl group constituting the oleophilicportion of the molecule, which confers solubility in the oil, isnormally a polyisobutylene group. Many examples of this type ofdispersant are well known commercially and in the literature. ExemplaryU.S. patents describing such dispersants are U.S. Pat. Nos. 3,172,892;3,215,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607;3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types ofdispersant are described in U.S. Pat. Nos. 3,036,003; 3,200,107;3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347;3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658;3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082;5,705,458. A further description of dispersants may be found, forexample, in European Patent Application No. 471 071, to which referenceis made for this purpose.

Hydrocarbyl-substituted succinic acid and hydrocarbyl-substitutedsuccinic anhydride derivatives are useful dispersants. In particular,succinimide, succinate esters, or succinate ester amides prepared by thereaction of a hydrocarbon-substituted succinic acid compound (e.g., ahydrocarbon-substituted succinic acid compound having at least 50 carbonatoms in the hydrocarbon substituent) with at least one equivalent of analkylene amine are particularly useful.

Succinimides are formed by the condensation reaction between hydrocarbylsubstituted succinic anhydrides and amines. Molar ratios can varydepending on the polyamine. For example, the molar ratio of hydrocarbylsubstituted succinic anhydride to TEPA can vary from about 1:1 to about5:1. Representative examples are shown in U.S. Pat. Nos. 3,087,936;3,172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800;and Canada Patent No. 1,094,044.

Succinate esters may be formed by the condensation reaction betweenhydrocarbyl substituted succinic anhydrides and alcohols or polyols.Molar ratios can vary depending on the alcohol or polyol used. Forexample, the condensation product of a hydrocarbyl substituted succinicanhydride and pentaerythritol is a useful dispersant.

Succinate ester amides may be formed by condensation reaction betweenhydrocarbyl substituted succinic anhydrides and alkanol amines. Forexample, suitable alkanol amines include ethoxylatedpolyalkylpolyamines, propoxylated polyalkylpolyamines andpolyalkenylpolyamines, such as polyethylene polyamines. One example ispropoxylated hexamethylenediamine. Representative examples are shown inU.S. Pat. No. 4,426,305.

The molecular weight of the hydrocarbyl substituted succinic anhydridesused in the preceding paragraphs can range between about 800 and about2,500 or more. The above products can be post-reacted with variousreagents such as sulfur, oxygen, formaldehyde, carboxylic acids, such asoleic acid. The above products can also be post reacted with boroncompounds, such as boric acid, borate esters or highly borateddispersants, to form borated dispersants, which may have from about 0.1to about 5 moles of boron per mole of dispersant reaction product.

Mannich base dispersants are made from the reaction of alkylphenols,formaldehyde, and amines. See U.S. Pat. No. 4,767,551, which isincorporated herein by reference. Process aids and catalysts, such asoleic acid and sulfonic acids, can also be part of the reaction mixture.Molecular weights of the alkylphenols may range from about 800 to about2,500. Representative examples are shown in U.S. Pat. Nos. 3,697,574;3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; and 3,803,039.

High molecular weight aliphatic acid modified Mannich condensationproducts useful in this disclosure can be prepared from high molecularweight alkyl-substituted hydroxyaromatics or HNR₂ group-containingreactants, wherein each R is independently selected from hydrogen,C1-C18 alkyl, aryl, alkenyl, alkaryl group.

Hydrocarbyl substituted amine ashless dispersant additives are wellknown to one skilled in the art; see, for example, U.S. Pat. Nos.3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084,197.

In certain embodiments, the dispersants include borated and/ornon-borated succinimides, including those derivatives frommono-succinimides, bis-succinimides, and/or mixtures of mono- andbis-succinimides, wherein the hydrocarbyl succinimide is derived from ahydrocarbylene group such as polyisobutylene having a Mn of from about500 to about 5000, or from about 1000 to about 3000, or about 1000 toabout 2000, or a mixture of such hydrocarbylene groups, often with highterminal vinylic groups. Other dispersants include succinic acid-estersand amides, alkylphenol-polyamine-coupled Mannich adducts, their cappedderivatives, and other related components.

Polymethacrylate or polyacrylate derivatives are another class ofdispersants. These dispersants may be prepared by reacting a nitrogencontaining monomer and a methacrylic or acrylic acid esters containingabout 5 to about 25 carbon atoms in the ester group. Representativeexamples are shown in U.S. Pat. Nos. 2,100,993, and 6,323,164.Polymethacrylate and polyacrylate dispersants may be used asmultifunctional viscosity modifiers. The lower molecular weight versionscan be used as lubricant dispersants or fuel detergents.

Illustrative dispersants useful in this disclosure include those derivedfrom polyalkenyl-substituted mono- or dicarboxylic acid, anhydride orester, wherein the polyalkenyl moiety has an average molecular weight ofat least about 900 and from greater than 1.3 to 1.7 (e.g. from greaterthan 1.3 to 1.6 or from greater than 1.3 to 1.5) functional groups(mono- or dicarboxylic acid producing moieties) per polyalkenyl moiety(a medium functionality dispersant). Functionality (F) can be determinedaccording to the following formula:

F=(SAP×Mn)/((112,200×A.I.)−(SAP×98)),

wherein: SAP is the saponification number (i.e., the number ofmilligrams of KOH consumed in the complete neutralization of the acidgroups in one gram of the succinic-containing reaction product, asdetermined according to ASTM D94); Mn is the number average molecularweight of the starting olefin polymer; and A.I. is the percent activeingredient of the succinic-containing reaction product (the remainderbeing unreacted olefin polymer, succinic anhydride and diluent).

The polyalkenyl moiety of the dispersant may have a number averagemolecular weight of at least about 900 or suitably at least about 1500,such as between about 1800 and about 3000 (e.g. between about 2000 andabout 2800, from about 2100 to about 2500, or from about 2200 to about2400). The molecular weight of a dispersant is generally expressed interms of the molecular weight of the polyalkenyl moiety. This is becausethe precise molecular weight range of the dispersant depends on numerousparameters including the type of polymer used to derive the dispersant,the number of functional groups, and the type of nucleophilic groupemployed.

Polymer molecular weight, specifically Mn, can be determined by variousknown techniques. One convenient method is gel permeation chromatography(GPC), which additionally provides molecular weight distributioninformation (see W. W. Yau, J. J. Kirkland and D. D. Bly, “Modern SizeExclusion Liquid Chromatography”, John Wiley and Sons, New York, 1979).Another useful method for determining molecular weight, particularly forlower molecular weight polymers, is vapor pressure osmometry (e.g., ASTMD3592).

In an embodiment, the polyalkenyl moiety in a dispersant has a narrowmolecular weight distribution (MWD), also referred to as polydispersity,as determined by the ratio of weight average molecular weight (Mw) tonumber average molecular weight (Mn). Polymers having a Mw/Mn of lessthan 2.2 (e.g. less than 2.0) are most desirable. Suitable polymers havea polydispersity of from about 1.5 to 2.1 (e.g. from about 1.6 to about1.8).

Suitable polyalkenes employed in the formation of the dispersantsinclude homopolymers, interpolymers or lower molecular weighthydrocarbons. One family of such polymers comprise polymers of ethyleneand/or at least one C3 to C26 alpha-olefin having the formula:

H₂C=CHR⁶,

wherein R⁶ is a straight or branched chain alkyl radical comprising 1 to26 carbon atoms and wherein the polymer contains carbon-to-carbonunsaturation, and a high degree of terminal ethenylidene unsaturation.In an embodiment, such polymers comprise interpolymers of ethylene andat least one alpha-olefin of the above formula, wherein R⁶ is alkyl offrom 1 to 18 carbon atoms (e.g. from 1 to 8 carbon atoms or from 1 to 2carbon atoms).

Another useful class of polymers is polymers prepared by cationicpolymerization of monomers such as isobutene and styrene. For example,the polymer(s) can be polyisobutenes obtained by polymerization of a C4refinery stream having a butene content of 35 to 75% by wt., and anisobutene content of 30 to 60% by wt. Petroleum feestreams, such asRaffinate II, can be a source of monomer for making poly-n-butenes.These feedstocks are disclosed in the art such as in U.S. Pat. No.4,952,739. Certain embodiments utilize polyisobutylene prepared from apure isobutylene stream or a Raffinate I stream to prepare reactiveisobutylene polymers with terminal vinylidene olefins. Polyisobutenepolymers that may be employed may be based on a polymer chain of fromabout 1500 to about 3000.

In yet further embodiments, the dispersant(s) are non-polymeric (e.g.,mono- or bis-succinimides). Such dispersants can be prepared byconventional processes, such as those disclosed in U.S. PatentApplication Publication No. 2008/0020950, the disclosure of which isincorporated herein by reference.

The dispersant(s) can be borated by conventional means, as generallydisclosed in U.S. Pat. Nos. 3,087,936, 3,254,025 and 5,430,105.

Dispersants may be used in an amount of zero to about 10 weight percentor about 0.01 to about 8 weight percent (e.g. about 0.1 to about 5weight percent or about 0.5 to about 3 weight percent). Or suchdispersants may be used in an amount of zero to about 8 weight percent(e.g. about 0.01 to about 5 weight percent or about 0.1 to about 3weight percent). On an active ingredient basis, such additives may beused in an amount of zero to about 10 weight percent (e.g. about 0.3 toabout 3 weight percent). The hydrocarbon portion of the dispersant atomscan range from about C60 to about C1000, or from about C70 to aboutC300, or from about C70 to about C200. These dispersants may containboth neutral and basic nitrogen, and mixtures thereof. Dispersants canbe end-capped by borates and/or cyclic carbonates. Nitrogen content inthe finished oil can vary from about zero to about 2000 ppm by weight(e.g. from about 100 ppm by weight to about 1200 ppm by weight). Basicnitrogen can vary from about zero to about 1000 ppm by weight (e.g. fromabout 100 ppm by weight to about 600 ppm by weight).

Dispersants as described herein are beneficially useful with thecompositions of the present disclosure. Further, in one embodiment,preparation of the compositions of the present disclosure using one ormore (e.g. 1, 2, 3, 4, or more) dispersants is achieved by combiningingredients of the present disclosure, plus optional base stocks andlubricant additives, in a mixture at a temperature above the meltingpoint of such ingredients, particularly that of the one or moreM-carboxylates (M=H, metal, two or more metals, mixtures thereof).

As used herein, the dispersant concentrations are given on an “asdelivered” basis. The active dispersant may be delivered with a processoil. The “as delivered” dispersant may contain from about 20 weightpercent to about 80 weight percent, or from about 40 weight percent toabout 60 weight percent, of active dispersant in the “as delivered”dispersant product.

Friction Modifier(s)

In any aspect or embodiment described herein, the composition of thepresent disclosure comprises at least one (e.g., 1, 2, 3, or 4, or more)friction modifier. A friction modifier is any material or materials thatcan alter the coefficient of friction of a surface lubricated by anylubricant or fluid containing such material(s). Friction modifiers, alsoknown as friction reducers, or lubricity agents or oiliness agents, andother such agents that change the ability of base oils, formulatedlubricant compositions, or functional fluids, to modify the coefficientof friction of a lubricated surface may be effectively used incombination with the base oils or lubricant compositions of the presentdisclosure if desired. Friction modifiers that lower the coefficient offriction are particularly advantageous in combination with the base oilsand lube compositions of this disclosure. Any friction modifier that isknown or that becomes know may be utilized in the composition of thepresent disclosure.

Friction modifiers may include, for example, organometallic compounds ormaterials, or mixtures thereof. Illustrative organometallic frictionmodifiers useful in the lubricating oil formulations of this disclosureinclude, for example, molybdenum amine, molybdenum diamine, anorganotungstenate, a molybdenum dithiocarbamate, molybdenumdithiophosphates, molybdenum amine complexes, molybdenum carboxylates,and the like, and mixtures thereof. In an embodiment, tungsten-basedcompounds are utilized.

Other illustrative friction modifiers useful in the lubricatingformulations of the present disclosure include, for example, alkoxylatedfatty acid esters, alkanolamides, polyol fatty acid esters, boratedglycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.

Illustrative alkoxylated fatty acid esters include, for example,polyoxyethylene stearate, fatty acid polyglycol ester, and the like.These can include polyoxypropylene stearate, polyoxybutylene stearate,polyoxyethylene isosterate, polyoxypropylene isostearate,polyoxyethylene palmitate, and the like.

Illustrative alkanolamides include, for example, lauric aciddiethylalkanolamide, palmic acid diethylalkanolamide, and the like.These can include oleic acid diethyalkanolamide, stearic aciddiethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylatedhydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.

Illustrative polyol fatty acid esters include, for example, glycerolmono-oleate, saturated mono-, di-, and tri-glyceride esters, glycerolmono-stearate, and the like. These can include polyol esters,hydroxyl-containing polyol esters, and the like.

Illustrative borated glycerol fatty acid esters include, for example,borated glycerol mono-oleate, borated saturated mono-, di-, andtri-glyceride esters, borated glycerol mono-sterate, and the like. Inaddition to glycerol polyols, these can include trimethylolpropane,pentaerythritol, sorbitan, and the like. These esters can be polyolmonocarboxylate esters, polyol dicarboxylate esters, and on occasionpolyoltricarboxylate esters. In certain embodiments, the frictionmodifier is glycerol mono-oleates, glycerol dioleates, glyceroltrioleates, glycerol monostearates, glycerol distearates, and glyceroltristearates and the corresponding glycerol monopalmitates, glyceroldipalmitates, glycerol tripalmitates, or the respective isostearates,linoleates, and the like, or combinations thereof. In an embodiment, thefriction modifier is a glycerol esters or mixtures containing any ofthese. Ethoxylated, propoxylated, butoxylated fatty acid esters ofpolyols, especially using glycerol as underlying polyol can be utilized.

Illustrative fatty alcohol ethers include, for example, stearyl ether,myristyl ether, and the like. Alcohols, including those that have carbonnumbers from C3 to C50, can be ethoxylated, propoxylated, or butoxylatedto form the corresponding fatty alkyl ethers. The underlying alcoholportion can be, e.g., stearyl, myristyl, C11-C13 hydrocarbon, oleyl,isosteryl, and the like.

Other friction modifiers could be optionally included in addition to thefatty phosphites and fatty imidazolines. A useful list of such otherfriction modifier additives is included in U.S. Pat. No. 4,792,410. U.S.Pat. No. 5,110,488 discloses metal salts of fatty acids and especiallyzinc salts, useful as friction modifiers. Fatty acids are also usefulfriction modifiers. A list of other suitable friction modifiers includesat least one of: (i) fatty phosphonates; (ii) fatty acid amides; (iii)fatty epoxides; (iv) borated fatty epoxides; (v) fatty amines; (vi)glycerol esters; (vii) borated glycerol esters; (viii) alkoxylated fattyamines; (ix) borated alkoxylated fatty amines; (x) metal salts of fattyacids; (xi) sulfurized olefins; (xii) condensation products ofcarboxylic acids or equivalents and polyalkylene-polyamines; (xiii)metal salts of alkyl salicylates; (xiv) amine salts of alkylphosphoricacids; (xv) fatty esters; (xvi) condensation products of carboxylicacids; or equivalents with polyols and mixtures thereof.

Representatives of each of these types of friction modifiers are knownand are commercially available. For instance, (i) includes components ofthe formulas:

(RO)2PHO,

(RO)(HO)PHO, and

P(OR)(OR)(OR),

wherein, in these structures, the each “R” is conventionally referred toas an alkyl group, but may also be hydrogen. It is, of course, possiblethat the alkyl group is actually alkenyl and thus the terms “alkyl” and“alkylated,” as used herein, will embrace other than saturated alkylgroups within the component. The component should have sufficienthydrocarbyl groups to render it substantially oleophilic. In someembodiments, the hydrocarbyl groups are substantially un-branched. Manysuitable such components are available commercially and may besynthesized as described in U.S. Pat. No. 4,752,416. In someembodiments, the component contains 8 to 24 carbon atoms in each of theR groups. In other embodiments, the component may be a fatty phosphitecontaining 12 to 22 carbon atoms in each of the fatty radicals, or 16 to20 carbon atoms. In one embodiment the fatty phosphite can be formedfrom oleyl groups, thus having 18 carbon atoms in each fatty radical.

The (iv) borated fatty epoxides are known from Canadian Patent No.1,188,704. These oil-soluble boron-containing compositions are preparedby reacting, at a temperature from 80° C. to 250° C., boric acid orboron trioxide with at least one fatty epoxide having the formula:

wherein each of R⁷, R⁸, R⁹ and R¹⁰ is independently hydrogen or analiphatic radical, or any two thereof together with the epoxy carbonatom or atoms to which they are attached, form a cyclic radical. In anembodiment, the fatty epoxide contains at least 8 carbon atoms.

The borated fatty epoxides can be characterized by the method for theirpreparation which involves the reaction of two materials. Reagent A canbe boron trioxide or any of the various forms of boric acid includingmetaboric acid (HBO₂), orthoboric acid (H₃BO₃) and tetraboric acid(H₂B₄O₇). In an embodiment, Reagent A is boric acid, such as orthoboricacid. Reagent B can be at least one fatty epoxide having the aboveformula. In the formula, each of the R groups is most often hydrogen oran aliphatic radical with at least one being a hydrocarbyl or aliphaticradical containing at least 6 carbon atoms. The molar ratio of reagent Ato reagent B may be about 1:0.25 to about 1:4 (e.g. about 1:1 to about1:3 or about 1:2). The borated fatty epoxides can be prepared by merelyblending the two reagents and heating them at temperature of about 80°C. to about 250° C., such as about 100° C. to about 200° C., for aperiod of time sufficient for reaction to take place. If desired, thereaction may be effected in the presence of a substantially inert,normally liquid organic diluent. During the reaction, water is evolvedand may be removed by distillation.

The (iii) non-borated fatty epoxides, corresponding to Reagent B above,are also useful as friction modifiers.

Borated amines are generally known from U.S. Pat. No. 4,622,158. Boratedamine friction modifiers (including (ix) borated alkoxylated fattyamines) can be prepared by the reaction of a boron compounds, asdescribed above, with the corresponding amines. The amine can be asimple fatty amine or hydroxy containing tertiary amines. The boratedamines can be prepared by adding the boron reactant, as described above,to an amine reactant and heating the resulting mixture at about 50° C.to about 300° C. (e.g. about 100° C. to about 250° C. or about 130° C.to about 180° C.) with stirring. The reaction is continued untilby-product water ceases to evolve from the reaction mixture indicatingcompletion of the reaction.

Among the amines useful in preparing the borated amines are commercialalkoxylated fatty amines known by the trademark “ETHOMEEN” and availablefrom Akzo Nobel. Representative examples of these ETHOMEEN™ materials isETHOMEEN™ C/12 (bis[2-hydroxyethyl]-coco-amine); ETHOMEEN™ C/20(polyoxyethylene-[10]cocoamine); ETHOMEEN™ S/12(bis[2-hydroxyethyl]-soyamine); ETHOMEEN™ T/12(bis[2-hydroxyethyl]-tallow-amine); ETHOMEEN™ T/15(polyoxyethylene-[5]tallowamine); ETHOMEEN™ O/12(bis[2-hydroxyethyl]oleyl-amine); ETHOMEEN™ 18/12(bis[2-hydroxyethyl]-octadecylamine); and ETHOMEEN™ 18/25(polyoxyethylene[15]-octadecylamine). Fatty amines and ethoxylated fattyamines are also described in U.S. Pat. No. 4,741,848. Dihydroxyethyltallowamine (commercially sold as ENT-12™) is included in these types ofamines.

The (viii) alkoxylated fatty amines, and (v) fatty amines themselves(such as oleylamine and dihydroxyethyl tallowamine) may be useful asfriction modifiers in this disclosure. Such amines are commerciallyavailable.

Both borated and unborated fatty acid esters of glycerol can be used asfriction modifiers. The (vii) borated fatty acid esters of glycerol areprepared by borating a fatty acid ester of glycerol with boric acid withremoval of the water of reaction. In an embodiment, there is sufficientboron present such that each boron will react with from 1.5 to 2.5hydroxyl groups present in the reaction mixture. The reaction may becarried out at a temperature in the range of about 60° C. to about 135°C., in the absence or presence of any suitable organic solvent, such asmethanol, benzene, xylenes, toluene, or oil.

The (vi) fatty acid esters of glycerol themselves can be prepared by avariety of methods well known in the art. Many of these esters, such asglycerol monooleate and glycerol tallowate, are manufactured on acommercial scale. In a particular embodiment, the esters are oil-solubleand prepared from C8 to C22 fatty acids or mixtures thereof, such as arefound in natural products and as are described in greater detail below.In an embodiment, fatty acid monoesters of glycerol used, although,mixtures of mono- and diesters may be used. For example, commercialglycerol monooleate may contain a mixture of 45% to 55% by weightmonoester and 55% to 45% diester.

Fatty acids can be used in preparing the above glycerol esters; they canalso be used in preparing their (x) metal salts, (ii) amides, and (xii)imidazolines, any of which can also be used as friction modifiers. In anembodiment, the fatty acids are those containing 10 to 24 carbon atoms,such as those containing 12 to 18 carbon atoms. The acids can bebranched or straight-chain, saturated or unsaturated. In someembodiments, the acids are straight-chain acids. In other embodiments,the acids are branched. Suitable acids include decanoic, oleic, stearic,isostearic, palmitic, myristic, palmitoleic, linoleic, lauric, andlinolenic acids, and the acids from the natural products tallow, palmoil, olive oil, peanut oil, corn oil, coconut oil and Neat's foot oil.In certain embodiments, the acid is oleic acid. In other embodiments,the metal salts include zinc and calcium salts. Examples are overbasedcalcium salts and basic oleic acid-zinc salt complexes, such as zincoleate, which can be represented by the formula Zn₄Oleate₆O₁. In anembodiment, the amides are those prepared by condensation with ammoniaor with primary or secondary amines such as ethylamine anddiethanolamine. Fatty imidazolines are the cyclic condensation productof an acid with a diamine or polyamine, such as a polyethylenepolyamine.The imidazolines may be represented by the structure:

wherein: R is an alkyl group; and R′ is hydrogen or a hydrocarbyl groupor a substituted hydrocarbyl group, including —(CH₂CH₂NH)_(n)— groups,wherein n is an integer from 1 to 4. In an embodiment, the frictionmodifier is the condensation product of a C10 to C24 fatty acid with apolyalkylene polyamine, and in particular, the product of isostearicacid with tetraethylenepentamine.

The condensation products of carboxylic acids and polyalkyleneamines(xiii) may be imidazolines or amides. They may be derived from any ofthe carboxylic acids described above and any of the polyamines describedherein.

Sulfurized olefins (xi) are well known commercial materials used asfriction modifiers. A particularly sulfurized olefin utilized herein isone which is prepared in accordance with the detailed teachings of U.S.Pat. Nos. 4,957,651 and 4,959,168. Described therein is a co-sulfurizedmixture of 2 or more reactants selected from the group consisting of (1)at least one fatty acid ester of a polyhydric alcohol, (2) at least onefatty acid, (3) at least one olefin, and (4) at least one fatty acidester of a monohydric alcohol. Reactant (3), the olefin component,comprises at least one olefin. This olefin is may be an aliphaticolefin, which usually will contain 4 to 40 carbon atoms, e.g. from 8 to36 carbon atoms. For example, terminal olefins, or alpha-olefins,including those having from 12 to 20 carbon atoms, may be utilized.Mixtures of these olefins are commercially available, and such mixturesare contemplated for use in this disclosure. The co-sulfurized mixtureof two or more of the reactants, is prepared by reacting the mixture ofappropriate reactants with a source of sulfur. The mixture to besulfurized can contain about 10 to about 90 parts of Reactant (1), orabout 0.1 to about 15 parts by weight of Reactant (2); or about 10 toabout 90 parts (e.g. about 15 to about 60 parts or about 25 to about 35parts) by weight of Reactant (3), or about 10 to about 90 parts byweight of reactant (4). The mixture, in the present disclosure, includesReactant (3) and at least one other member of the group of reactantsidentified as Reactants (1), (2) and (4). The sulfurization reaction maybe effected at an elevated temperature with agitation and optionally inan inert atmosphere and in the presence of an inert solvent. Thesulfurizing agents useful in the process of the present disclosureinclude elemental sulfur, which may be hydrogen sulfide, sulfur halideplus sodium sulfide, and a mixture of hydrogen sulfide and sulfur orsulfur dioxide. For example, about 0.5 to about 3 moles of sulfur areemployed per mole of olefinic bonds. Sulfurized olefins may also includesulfurized oils, such as vegetable oil, lard oil, oleic acid and olefinmixtures.

Metal salts of alkyl salicylates (xiii) include calcium and other saltsof long chain (e.g. C12 to C16) alkyl-substituted salicylic acids.

Amine salts of alkylphosphoric acids (xiv) include salts of oleyl andother long chain esters of phosphoric acid, with amines as describedbelow. Useful amines in this regard are tertiary-aliphatic primaryamines, sold under the tradename Primene™.

In some embodiments, the friction modifier is a fatty acid or fatty oil,a metal salt of a fatty acid, a fatty amide, a sulfurized fatty oil orfatty acid, an alkyl phosphate, an alkyl phosphate amine salt; acondensation product of a carboxylic acid and a polyamine, a boratedfatty epoxide, a fatty imidazoline, or combinations thereof.

In other embodiments, the friction modifier may be the condensationproduct of isostearic acid and tetraethylene pentamine, the condensationproduct of isostearic acid and 1-[tris(hydroxymethyl)]methylamine,borated polytetradecyloxirane, zinc oleate, hydroxylethyl-2-heptadecenylimidazoline, dioleyl hydrogen phosphate, C14-C18 alkyl phosphate or theamine salt thereof, sulfurized vegetable oil, sulfurized lard oil,sulfurized oleic acid, sulfurized olefins, oleyl amide, glycerolmonooleate, soybean oil, or mixtures thereof.

In still other embodiments, the friction modifier may be glycerolmonooleate, oleylamide, the reaction product of isostearic acid and2-amino-2-hydroxymethyl-1,3-propanediol, sorbitan monooleate,9-octadecenoic acid, isostearyl amide, isostearyl monooleate orcombinations thereof.

Although their presence is not required to obtain the benefit of thepresent disclosure, friction modifiers may be present in an amount fromzero to about 2 wt. % (e.g., about 0.01 wt. % to about 1.5 wt. %) of thecomposition of the present disclosure. These ranges may apply to theamounts of individual friction modifier present in the composition or tothe total friction modifier component in the compositions, which mayinclude a mixture of two or more friction modifiers.

Many friction modifiers tend to also act as emulsifiers. This is oftendue to the fact that friction modifiers often have non-polar fatty tailsand polar head groups.

The composition of the present disclosure exhibits desired properties,e.g., wear control, in the presence or absence of a friction modifier.

Although their presence is not required to obtain the benefit of thisdisclosure, the friction modifier or friction modifiers may be presentin an amount of about 0.01 weight percent to about 5 weight percent(e.g. about 0.1 weight percent to about 2.5 weight percent, or about 0.1weight percent to about 1.5 weight percent, or about 0.1 weight percentto about 1 weight percent). Concentrations of molybdenum-containingmaterials are often described in terms of Mo metal concentration.Advantageous concentrations of Mo may range from about 25 ppm to about700 ppm or more (e.g. about 50 to about 200 ppm). Friction modifiers ofall types may be used alone or in mixtures with the materials of thisdisclosure. Often mixtures of two or more friction modifiers, ormixtures of friction modifier(s) with alternate surface activematerial(s), are also desirable.

Molybdenum-Containing Compounds (Friction Reducers)

Illustrative molybdenum-containing friction reducers useful in thedisclosure include, for example, an oil-soluble decomposable organomolybdenum compound, such as Molyvan™ 855 which is an oil solublesecondary diarylamine defined as substantially free of active phosphorusand active sulfur. The Molyvan™ 855 is described in Vanderbilt'sMaterial Data and Safety Sheet as an organo molybdenum compound having adensity of 1.04 and viscosity at 100° C. of 47.12 cSt. The organomolybdenum compounds may be useful because of their superior solubilityand effectiveness.

Another illustrative molybdenum-containing compound is Molyvan™ L, whichis sulfonated oxymolybdenum dialkyldithiophosphate described in U.S.Pat. No. 5,055,174 hereby incorporated by reference.

Molyvan™ A made by R. T. Vanderbilt Company, Inc., New York, N.Y., USA,is also an illustrative molybdenum-containing compound, which containsabout 28.8 wt. % Mo, 31.6 wt. % C, 5.4 wt. % H., and 25.9 wt. % S. Alsouseful are Molyvan™ 855, Molyvan™ 822, Molyvan™ 856, and Molyvan™ 807.

Also useful is Sakura Lube™ 500, which is more soluble Modithiocarbamate containing lubricant additive obtained from Asahi DenkiCorporation and comprised of about 20.2 wt. % Mo, 43.8 wt. % C, 7.4 wt.% H, and 22.4 wt. % S. Sakura Lube™ 300, a low sulfur molybdenumdithiophosphate having a molybdenum to sulfur ratio of 1:1.07, is amolybdenum-containing compound useful in this disclosure.

Also useful is Molyvan™ 807, a mixture of about 50 wt. % molybdenumditridecyldithyocarbonate, and about 50 wt. % of an aromatic oil havinga specific gravity of about 38.4 SUS and containing about 4.6 wt. %molybdenum, also manufactured by R. T. Vanderbilt and marketed as anantioxidant and antiwear additive.

Other sources are molybdenum Mo(Co)₆, and molybdenum octoate,MoO(C₇H₁₅CO₂)₂ containing about 8 wt-% Mo marketed by Aldrich ChemicalCompany, Milwaukee, Wis. and molybdenum naphthenethioctoate marketed byShephard Chemical Company, Cincinnati, Ohio.

Inorganic molybdenum compounds, such as molybdenum sulfide andmolybdenum oxide, are substantially less preferred than the organiccompounds as described in Molyvan™ 855, Molyvan™ 822, Molyvan™ 856, andMolyvan™ 807.

Illustrative molybdenum-containing compounds useful in this disclosureare disclosed, for example, in U.S. Patent Application Publication No.2003/0119682, which is incorporated herein by reference.

Organo molybdenum-nitrogen complexes may also be included in theformulations of the present disclosure. The term “organo molybdenumnitrogen complexes” embraces the organo molybdenum nitrogen complexesdescribed in U.S. Pat. No. 4,889,647. The complexes are reactionproducts of a fatty oil, dithanolamine and a molybdenum source. Specificchemical structures have not been assigned to the complexes. U.S. Pat.No. 4,889,647 reports an infrared spectrum for an exemplary reactionproduct of that disclosure; the spectrum identifies an ester carbonylband at 1740 cm 1 and an amide carbonyl band at 1620 cm 1. The fattyoils are glyceryl esters of higher fatty acids containing at least 12carbon atoms up to 22 carbon atoms or more. The molybdenum source is anoxygen-containing compound such as ammonium molybdates, molybdenumoxides and mixtures.

Other organo molybdenum complexes which can be used in the presentdisclosure are tri nuclear molybdenum sulfur compounds described in EP 1040 115 and WO 99/31113, and the molybdenum complexes described in U.S.Pat. No. 4,978,464.

Although their presence is not required to obtain the benefit of thepresent disclosure, molybdenum-containing additives may be used in anamount of from zero to about 5.0 (e.g., ≤ about 5, ≤ about 4, ≤ about 3,≤ about 2, or ≤ about 1) percent by mass of the composition of thepresent disclosure. For example, the dosage may be up to about 3,000 ppmby mass, such as from about 100 ppm to about 2,500 ppm by mass, fromabout 300 to about 2,000 ppm by mass, or from about 300 to about 1,500ppm by mass of molybdenum.

Borated Ester Compounds (Corrosion Inhibitors)

In any aspect or embodiment described herein, the composition of thepresent disclosure can have at least one (e.g., 1, 2, 3, or 4, or more)borated-ester compound. Illustrative boron-containing compounds usefulin the disclosure include, for example, a borate ester, a boric acid,other boron compounds, such as a boron oxide. The boron compound ishydrolytically stable and is utilized for improved antiwear and performsas a rust and corrosion inhibitor for copper bearings and other metalengine components. The borated ester compound acts as an inhibitor forcorrosion of metal to prevent corrosion of either ferrous or non-ferrousmetals (e.g. copper, bronze, brass, titanium, aluminum and the like) orboth, present in concentrations in which they are effective ininhibiting corrosion.

Patents describing techniques for making basic salts of sulfonic,carboxylic acids and mixtures thereof include U.S. Pat. Nos. 5,354,485;2,501,731; 2,616,911; 2,777,874; 3,384,585; 3,320,162; 3,488,284; and3,629,109. The disclosures of these patents are incorporated herein byreference. Methods of preparing borated overbased compositions are foundin U.S. Pat. Nos. 4,744,920; 4,792,410; and PCT publication WO 88/03144.The disclosures of these references are incorporated herein byreference. The oil-soluble neutral or basic salts of alkali or alkalineearth metals salts may also be reacted with a boron compound.

An illustrative borate ester utilized in this disclosure is manufacturedby Exxon-Mobil USA under the product designation of (“MCP 1286”) andMOBIL ADC700. Test data show the viscosity at 100° C. using the D-445method is 2.9 cSt; the viscosity at 40° C. using the D-445 method is11.9; the flash point using the D-93 method is 146; the pour point usingthe D-97 method is -69; and the percent boron as determined by the ICPmethod is 5.3%. The borated ester (Vanlube™ 289), which is marketed asan antiwear/antiscuff additive and friction reducer, is an exemplaryborate ester useful in the disclosure.

An illustrative borate ester useful in this disclosure is the reactionproduct obtained by reacting about 1 mole fatty oil, about 1.0 to 2.5moles diethanolamine followed by subsequent reaction with boric acid toyield about 0.1 to 3 percent boron by mass. It is believed that thereaction products may include one or both of the following two primarycomponents, with the further listed components being possible componentswhen the reaction is pushed toward full hydration:

wherein Y represents a fatty oil residue. In an embodiment, the fattyoils are glyceryl esters of higher fatty acids containing at least 12carbon atoms (e.g. 22 carbon atoms or more). Such esters are commonlyknown as vegetable and animal oils. Vegetable oils that may be usedinclude oils derived from coconut, corn, cottonseed, linseed, peanut,soybean and sunflower seed. Similarly, animal fatty oils such as tallowmay be used.

The source of boron is boric acid or materials that afford boron and arecapable of reacting with the intermediate reaction product of fatty oiland diethanolamine to form a borate ester composition.

While the above organoborate ester composition is specifically discussedabove, it should be understood that other organoborate estercompositions should also function with similar effect in the presentdisclosure, such as those set forth in U.S. Patent ApplicationPublication No. 2003/0119682, which is incorporated herein by reference.In addition, dispersions of borate salts, such as potassium borate, mayalso be useful.

Other illustrative organoborate compositions useful in this disclosureare disclosed, for example, in U.S. Patent Application Publication No.2008/0261838, which is incorporated herein by reference.

In addition, other illustrative organoborate compositions useful in thisdisclosure are disclosed, for example, U.S. Pat. Nos. 4,478,732,4,406,802, 4,568,472 on borated mixed hydroxyl esters, alkoxylatedamides, and amines; U.S. Pat. No. 4,298,486 on borated hydroxyethylimidazolines; U.S. Pat. No. 4,328,113 on borated alkyl amines and alkyldiamines; U.S. Pat. No. 4,370,248 on borated hydroxyl-containing esters,including GMO; U.S. Pat. No. 4,374,032 on borated hydroxyl-containinghydrocarbyl oxazolines; U.S. Pat. No. 4,376,712 on borated sorbitanesters; U.S. Pat. No. 4,382,006 on borated ethoxylated amines; U.S. Pat.No. 4,389,322 on ethoxylated amides and their borates; U.S. Pat. No.4,472,289 on hydrocarbyl vicinal diols and alcohols and ester mixturesand their borates; U.S. Pat. No. 4,522,734 on borates of hydrolyzedhydrocarbyl epoxides; U.S. Pat. No. 4,537,692 on etherdiamine borates;U.S. Pat. No. 4,541,941 on mixtures containing vicinal diols andhydroxyl substituted esters and their borates; U.S. Pat. No. 4,594,171on borated mixtures of various hydroxyl and/or nitrogen containingborates; and U.S. Pat. No. 4,692,257 on various borated alcohols/diols,all of which are incorporated herein by reference.

Although their presence is not required to obtain the benefit of thisdisclosure, boron-containing compounds may be present in an amount offrom zero to about 10.0% percent (e.g. from about 0.01% to about 5% orfrom about 0.1% to about 3.0%) by weight of the composition of thepresent disclosure. An effective elemental boron range of up to about1000 ppm or less than about 1% elemental boron. Thus, in an embodiment,a concentration of elemental boron is from about 100 to about 1000 ppm(e.g. from about 100 to about 300 ppm).

When the grease composition of the present disclosure includes one ormore of the additives discussed herein, the additive(s) are blended intothe composition in an amount sufficient for it to perform its intendedfunction.

The weight percent (wt. %) indicated herein is based on the total weightof the composition of the present disclosure. It is noted that many ofthe additives are shipped from the additive manufacturer as aconcentrate, containing one or more additives together, with a certainamount of base oil diluents. Accordingly, the weight amounts mentionedherein are directed to the amount of active ingredient (that is thenon-diluent portion of the ingredient).

The grease of the present disclosure may be made in a batch process withcontactor followed by finishing kettle or in a continuous grease makingprocess, both of which are well known and widely used. In batch greasemaking, the grease is usually prepared by chemically reacting andmechanically dispersing the thickener components in the lubricating oilfor from about 1 to about 8 hours or more (e.g., from about 3 to about 6hours) followed by heating at elevated temperature (e.g., from about140° C. to about 225° C. depending upon the particular thickener used)until the mixture thickens. In some cases, a preformed thickener can beused. The mixture is then cooled to ambient temperature (typically about60° C.) during which time performance additive(s) or additive package isadded.

The grease composition can be mixed, blended, or milled in any number ofways including external mixers, roll mills, internal mixers, Banburymixers, screw extruders, augers, colloid mills, homogenizers, and thelike. A continuous grease making process is described to U.S. Pat. No.7,829,512.

The grease composition may further comprise, as described herein, atleast one performance additive selected from the group consisting ofanticorrosive agent or corrosion inhibitor, an extreme pressureadditive, an antiwear agent, a pour point depressants, an antioxidant oroxidation inhibitor, a rust inhibitor, a metal deactivator, adispersant, a demulsifier, a dye or colorant/chromophoric agent, a sealcompatibility agent, a friction modifier, a viscosity modifier/improver,a viscosity index improver, or combinations thereof.

The present disclosure is further illustrated by the following examples,which should not be construed as limiting. The data below demonstratesthat the compositions of the present disclosure provide the surprisingand unexpected effect of having significantly improved structuralstability and resistance to breaking down, relative to other greases,under high temperature conditions. Those skilled in the art willrecognize that the disclosure may be practiced with variations on thedisclosed structures, materials, compositions and methods, and suchvariations are regarded as within the ambit of the disclosure.

Examples

Grease formulations were prepared as described herein. All of theingredients used herein are commercially available.

The performance additive package used in the grease formulationsincluded conventional additives in conventional amounts. Conventionaladditives used in the formulations were one or more of an anticorrosiveagent or corrosion inhibitor, an extreme pressure additive, an antiwearagent, a pour point depressants, an antioxidant or oxidation inhibitor,a rust inhibitor, a metal deactivator, a dispersant, a demulsifier, adye or colorant/chromophoric agent, a seal compatibility agent, afriction modifier, a viscosity modifier/improver, and a viscosity indeximprover.

The grease formulations were tested for high temperature properties inaccordance with the DIN 51821 (FAG FE9) test method.

The grease formulations were tested for structural stability andresistance to breaking down under high temperature conditions inaccordance with the DIN 51821 (FAG FE9) test method.

The grease formulations were tested for frictional properties using aMini-Traction Machine (MTM) at 100° C., 1.0 GPa, 50% slide/roll ratio(SRR), and 3.0 m/s-0 m/s. Coefficient of friction was determined.

A first stage investigation was conducted for formulating and processinggrease thickeners. The performance testing was compared to the followingthickeners: Part A is a sample in which the isocyanate is solely reactedwith an alicyclic amine. Part B is a sample in which the isocyanate issolely reacted with an aliphatic amine. Each of the new samplecandidates were compared with the samples formulated with conventionalMDI isocyanate. These particular samples are crowned with either a B oran A. The first stage formulations are shown in FIG. 1. Test results forthe first stage formulations are shown in FIG. 2. The test results forthe first stage formulations included worked penetration in accordancewith ASTM D217-17, shell roll in accordance with ASTM D1403, anddropping point in accordance with ASTM D2265.

A second stage investigation was conducted for formulating andprocessing grease thickeners. For this second stage investigation, eachisocyanate prepolymer was reacted with both of primary amines, namely analicyclic amine and an aliphatic amine. The combination of both aminesis similar to the Polyrex EM thickener system. Combining both amines tothe isocyanate component gives a much superior thickener than eitherPart A or Part B. Enhanced properties were shown by combining the MDIthickener chemistry with the isocyanate prepolymer thickener chemistry.

Worked penetration test results for the second stage formulations inaccordance with ASTM D217-17 are graphically shown in FIG. 3. Workedpenetration should be an NLGI 2 Grade or an NLGI 3 Grade. The red linerepresents the maximum range of the worked penetration of an NLGI2-Grade.

Shell roll test results for the second stage formulations in accordancewith ASTM D1403 are graphically shown in FIG. 4. A delta of 30 point isan average for an ASTM D217 100K.

Dropping point test results for the second stage formulations inaccordance with ASTM D2265 are graphically shown in FIG. 5. The minimumdropping point for Polyrex EM is 250° C.

The following Stribeck analysis using the MTM machine providescomparative information between the isocyanate prepolymer grease samplescompared to commercial Polyrex EM. The sample candidates and testconditions for the traction time and Stribeck testing are as follows:

14-067635-19 Finished Polyrex EM

17-13001 Finished grease fundamentals thickener Part A MP 102 plus PartB 5030, blend 50/50

17-13000 Finished grease fundamentals thickener Part A MP 102 plus PartB MP 102, blend 50/50

17-12573 Finished grease fundamentals thickener Part A 5030 plus Part BMP 102, blend 50/50

17-12566 Finished grease fundamentals thickener Part A 5030 plus Part B5030, blend 50/50

16-97778 Finished grease fundamentals thickener Part A MP 102 plus PartB 5030, blend 50/50

16-97777 Finished grease fundamentals thickener Part A MP 102 plus PartB MP 102, blend 50/50

16-97776 Finished grease fundamentals thickener Part A 5030 plus Part BMP 102, blend 50/50

The traction time and Stribeck test conditions were as follows:

Traction Time Step Conditions: 100° C., 1.0 GPa, 50% SRR, 50 mm/s, 2 hr.

Stribeck Test Conditions: 100° C., 1.0 GPa, 50% SRR, 3.0 m/s-0 m/s.

FIG. 6 graphically shows a Stribeck analysis for the grease formulationcontaining thickener Part A 5030 plus Part B 5030, blend 50/50.

FIG. 7 graphically shows a Stribeck analysis for the grease formulationcontaining thickener Part A 5030 plus Part B MP 102, blend 50/50.

FIG. 8 graphically shows a Stribeck analysis for the grease formulationcontaining thickener Part A MP 102 plus Part B MP 102, blend 50/50.

FIG. 9 graphically shows a Stribeck analysis for the grease formulationcontaining thickener Part A MP 102 plus Part B 5030, blend 50/50.

FIG. 10 graphically shows a Stribeck analysis for the commercial greaseformulation Polyrex EM.

FIG. 11 shows high temperature properties for the second stageformulations in accordance with the DIN 51821 (FAG FE9) test method. Thetest conditions were 160° C., Variation B, 6000 rpm, 1.5 kg axial load.

As shown in the examples, the polyurea grease compositions of thisdisclosure perform well in high temperature environments and provide alonger application life as well as reduce friction and wear in the metalparts that the grease is lubricating, thereby leading to better energyefficiency and equipment reliability and life.

PCT and EP Clauses:

1. A grease composition comprising: at least one base oil; and at leastone polyurea thickener; wherein said at least one polyurea thickener isprepared by reacting an isocyanate-terminated prepolymer with at leastone amine under reaction conditions sufficient to prepare said at leastone polyurea thickener; and wherein said isocyanate-terminatedprepolymer is prepared by reacting a polyisocyanate with a polyol, at anNCO/OH equivalent ratio of 1.05:1 to 10:1, under reaction conditionssufficient to prepare said isocyanate-terminated prepolymer.

2. The grease composition of clause 1 wherein said isocyanate-terminatedprepolymer has an isocyanate content of 0.5 to 40 weight percent, basedon the weight of the isocyanate-terminated prepolymer after reaction.

3. The grease composition of clauses 1 and 2 wherein the polyisocyanateis selected from the group consisting of 2,4-toluene diisocyanate (TDI);2,6-toluene diisocyanate (TDI); 4,4′-diisocyanatodiphenylmethane (MDI);p-phenylene diisocyanate (PPDI); diphenyl-4,4′-diisocyanate;dibenzyl-4,4′-diisocyanate; stilbene-4,4′-diisocyanate;benzophenone-4,4′-diisocyanate; 1,3- and 1,4-xylene diisocyanate; andmixtures thereof.

4. The grease composition of clauses 1-3 wherein the polyisocyanate isselected from the group consisting of 1,6-hexamethylene diisocyanate(HDI); 1,3-cyclohexyl diisocyanate; 1,4-cyclohexyl diisocyanate (CHDI);saturated diphenylmethane diisocyanate H(12)MDI;bis{4-isocyanatocyclohexyl}methane; 4,4′-methylene dicyclohexyldiisocyanate; 4,4-methylene bis (dicyclohexyl)diisocyanate; methylenedicyclohexyl diisocyanate; methylene bis (4-cyclohexylene isocyanate);saturated methylene diphenyl diisocyanate; saturated methyl diphenyldiisocyanate; isophorone diisocyanate (IPDI); hexamethylene diisocyanate(HDI); 2,2,4-trimethyl-1,6-hexamethylene diisocyanate2,4,4-trimethyl-1,6-hexamethylene diisocyanate; dodecamethylenediisocyanate; 1,4-diisocyanatocyclohexane;1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane (IPDI); 2,4′-and/or 4,4′-diisocyanato-dicyclohexyl methane; 2,4-diisocyanato-diphenylmethane; 4,4′-diisocyanato-diphenyl methane; 2,4-diisocyanatotoluene;2,6-diisocyanatotoluene; and mixtures of these isomers with their higherhomologues.

5. The grease composition of clauses 1-4 wherein the polyisocyanate isselected from the group consisting of hexamethylene diisocyanate (HDI);2,2,4-trimethyl-1,6-hexamethylene diisocyanates;2,4,4-trimethyl-1,6-hexamethylene diisocyanate; dodecamethylenediisocyanate; 1,4-diisocyanatocyclohexane;1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane;2,4′-diisocyanato-dicyclohexyl methane; 4,4′-diisocyanato-dicyclohexylmethane; 2,4-diisocyanato-diphenyl methane; 4,4′-diisocyanato-diphenyl2,4-diisocyanatotoluene; 2,6-diisocyanatotoluene; and any mixtures ofthese compounds and their higher homologues.

6. The grease composition of clauses 1-5 wherein the polyol is selectedfrom the group consisting of polyester polyols, polycaprolactonepolyols, and polyether polyols.

7. The grease composition of clauses 1-6 wherein the polyol is selectedfrom the group consisting of polyester polyols, polycaprolactonepolyols, polyether polyols, polyhydroxy polycarbonates, polyhydroxypolyacetals, polyhydroxy polyacrylates, polyhydroxy polyester amides andpolyhydroxy polythioethers or mixtures thereof; wherein said polyolshave at least two hydroxyl groups per molecule and have a hydroxyl groupcontent of 0.5 to 20 weight percent.

8. The grease composition of clauses 1-7 wherein the polyol is selectedfrom the group consisting of polyester polyols, polycaprolactonepolyols, polyether polyols, polytetramethylene ether glycol, polyhydroxypolycarbonates, polyhydroxy polyacetals, polyhydroxy polyacrylates,polyhydroxy polyester amides and polyhydroxy polythioethers, or mixturesthereof.

9. The grease composition of clauses 1-8 wherein theisocyanate-terminated prepolymer is selected from the group consistingof TDI-ether, TDI-ester, TDI-lactone, MDI-ether, MDI-ester, MDI-lactone,H(12)MDI-ether, H(12)MDI-ester, H(12)MDI-lactone, HDI-ether, HDI-ester,HDI-lactone, IPDI-ether, IPDI-ester, IPDI-lactone, PPDI-ether,PPDI-ester, PPDI-lactone, and mixtures thereof.

10. The grease composition of clauses 1-9 wherein the amine is selectedfrom the group consisting of pentylamine, hexylamine, heptylamine,octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine,octadecylamine, eicosylamine, dodecenylamine, hexadecenylamine,octadecenylamine, octadecadienylamine, abietylamine, aniline, toluidine,naphthylamine, cumylamine, bomylamine, fenchylamine, tertiary butylaniline, benzylamine, 3-phenethylamine, stearylamine, laurylamine,palmitylamine, oleylamine, petroselinylamine, linoleylamine,linolenylamine, eleostearylamine, cyclohexylamine, primary tallow amine,ethylenediamine, propanediamine, butanediamine, hexanediamine,dodecanediamine, octanediamine, hexadecanediamine, cyclohexanediamine,cyclooctanediamine, phenylenediamine, tolylenediamine, xylylenediamine,dianiline methane, ditoluidinemethane, bis(aniline), bis(toluidine),piperazine, and mixtures thereof.

11. The grease composition of clauses 1-10 wherein, when used under hightemperature conditions, high temperature performance in accordance withDIN 51821 (FAG FE9) is improved, as compared to high temperatureperformance achieved using a grease composition containing other thansaid polyurea thickener.

12. The grease composition of clauses 1-11 wherein structural stabilityand resistance to breaking down is improved when tested under hightemperature conditions in accordance with DIN 51821 (FAG FE9), ascompared to structural stability and resistance to breaking downachieved using a grease composition containing other than said polyureathickener.

13. The grease composition of clauses 1-12 wherein, when tested using aMini-Traction Machine (MTM) at 100° C., 1.0 GPa, 50% slide/roll ratio(SRR), and 3.0 m/s-0 m/s, coefficient of friction is improved, ascompared to coefficient of friction achieved using a grease compositioncontaining other than said polyurea thickener.

14. A method of preparing a grease composition comprising mixing atleast one base oil, and at least one polyurea thickener; wherein said atleast one polyurea thickener is prepared by reacting anisocyanate-terminated prepolymer with at least one amine under reactionconditions sufficient to prepare said at least one polyurea thickener;and wherein said isocyanate-terminated prepolymer is prepared byreacting a polyisocyanate with a polyol, at an NCO/OH equivalent ratioof 1.05:1 to 10:1, under reaction conditions sufficient to prepare saidisocyanate-terminated prepolymer.

15. A method for improving high temperature performance of a greasecomposition in a mechanical component lubricated with the greasecomposition, said method comprising using a grease compositioncomprising: at least one base oil; and at least one polyurea thickener;wherein said at least one polyurea thickener is prepared by reacting anisocyanate-terminated prepolymer with at least one amine under reactionconditions sufficient to prepare said at least one polyurea thickener;and wherein said isocyanate-terminated prepolymer is prepared byreacting a polyisocyanate with a polyol, at an NCO/OH equivalent ratioof 1.05:1 to 10:1, under reaction conditions sufficient to prepare saidisocyanate-terminated prepolymer.

All patents and patent applications, test procedures (such as ASTMmethods, UL methods, and the like), and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with this disclosure and for all jurisdictions in whichsuch incorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.While the illustrative embodiments of the disclosure have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of thedisclosure. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present disclosure,including all features which would be treated as equivalents thereof bythose skilled in the art to which the disclosure pertains.

The present disclosure has been described above with reference tonumerous embodiments and specific examples. Many variations will suggestthemselves to those skilled in this art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims.

1. A grease composition comprising: at least one base oil; and at leastone polyurea thickener; wherein said at least one polyurea thickener isprepared by reacting an isocyanate-terminated prepolymer with at leastone amine under reaction conditions sufficient to prepare said at leastone polyurea thickener; and wherein said isocyanate-terminatedprepolymer is prepared by reacting a polyisocyanate with a polyol, at anNCO/OH equivalent ratio of 1.05:1 to 10:1, under reaction conditionssufficient to prepare said isocyanate-terminated prepolymer.
 2. Thegrease composition of claim 1 wherein said isocyanate-terminatedprepolymer has an isocyanate content of 0.5 to 40 weight percent, basedon the weight of the isocyanate-terminated prepolymer after reaction. 3.The grease composition of claim 1 wherein the polyisocyanate is selectedfrom the group consisting of 2,4-toluene diisocyanate (TDI); 2,6-toluenediisocyanate (TDI); 4,4′-diisocyanatodiphenylmethane (MDI); p-phenylenediisocyanate (PPDI); diphenyl-4,4′-diisocyanate;dibenzyl-4,4′-diisocyanate; stilbene-4,4′-diisocyanate;benzophenone-4,4′-diisocyanate; 1,3- and 1,4-xylene diisocyanate; andmixtures thereof.
 4. The grease composition of claim 1 wherein thepolyisocyanate is selected from the group consisting of1,6-hexamethylene diisocyanate (HDI); 1,3-cyclohexyl diisocyanate;1,4-cyclohexyl diisocyanate (CHDI); saturated diphenylmethanediisocyanate H(12)MDI; bis{4-isocyanatocyclohexyl}methane;4,4′-methylene dicyclohexyl diisocyanate; 4,4-methylene bis(dicyclohexyl)diisocyanate; methylene dicyclohexyl diisocyanate;methylene bis (4-cyclohexylene isocyanate); saturated methylene diphenyldiisocyanate; saturated methyl diphenyl diisocyanate; isophoronediisocyanate (IPDI); hexamethylene diisocyanate (HDI);2,2,4-trimethyl-1,6-hexamethylene diisocyanate2,4,4-trimethyl-1,6-hexamethylene diisocyanate; dodecamethylenediisocyanate; 1,4-diisocyanatocyclohexane;1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane (IPDI); 2,4′-and/or 4,4′-diisocyanato-dicyclohexyl methane; 2,4-diisocyanato-diphenylmethane; 4,4′-diisocyanato-diphenyl methane; 2,4-diisocyanatotoluene;2,6-diisocyanatotoluene; and mixtures of these isomers with their higherhomologues.
 5. The grease composition of claim 1 wherein thepolyisocyanate is selected from the group consisting of hexamethylenediisocyanate (HDI); 2,2,4-trimethyl-1,6-hexamethylene diisocyanates;2,4,4-trimethyl-1,6-hexamethylene diisocyanate; dodecamethylenediisocyanate; 1,4-diisocyanatocyclohexane;1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane;2,4′-diisocyanato-dicyclohexyl methane; 4,4′-diisocyanato-dicyclohexylmethane; 2,4-diisocyanato-diphenyl methane; 4,4′-diisocyanato-diphenyl2,4-diisocyanatotoluene; 2,6-diisocyanatotoluene; and any mixtures ofthese compounds and their higher homologues.
 6. The grease compositionof claim 1 wherein the polyol is selected from the group consisting ofpolyester polyols, polycaprolactone polyols, and polyether polyols. 7.The grease composition of claim 1 wherein the polyol is selected fromthe group consisting of polyester polyols, polycaprolactone polyols,polyether polyols, polyhydroxy polycarbonates, polyhydroxy polyacetals,polyhydroxy polyacrylates, polyhydroxy polyester amides and polyhydroxypolythioethers or mixtures thereof; wherein said polyols have at leasttwo hydroxyl groups per molecule and have a hydroxyl group content of0.5 to 20 weight percent.
 8. The grease composition of claim 1 whereinthe polyol is selected from the group consisting of polyester polyols,polycaprolactone polyols, polyether polyols, polytetramethylene etherglycol, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxypolyacrylates, polyhydroxy polyester amides and polyhydroxypolythioethers, or mixtures thereof.
 9. The grease composition of claim1 wherein the isocyanate-terminated prepolymer is selected from thegroup consisting of TDI-ether, TDI-ester, TDI-lactone, MDI-ether,MDI-ester, MDI-lactone, H(12)MDI-ether, H(12)MDI-ester,H(12)MDI-lactone, HDI-ether, HDI-ester, HDI-lactone, IPDI-ether,IPDI-ester, IPDI-lactone, PPDI-ether, PPDI-ester, PPDI-lactone, andmixtures thereof.
 10. The grease composition of claim 1 wherein theamine is selected from the group consisting of pentylamine, hexylamine,heptylamine, octylamine, decylamine, dodecylamine, tetradecylamine,hexadecylamine, octadecylamine, eicosylamine, dodecenylamine,hexadecenylamine, octadecenylamine, octadecadienylamine, abietylamine,aniline, toluidine, naphthylamine, cumylamine, bomylamine, fenchylamine,tertiary butyl aniline, benzylamine, β-phenethylamine, stearylamine,laurylamine, palmitylamine, oleylamine, petroselinylamine,linoleylamine, linolenylamine, eleostearylamine, cyclohexylamine,primary tallow amine, ethylenediamine, propanediamine, butanediamine,hexanediamine, dodecanediamine, octanediamine, hexadecanediamine,cyclohexanediamine, cyclooctanediamine, phenylenediamine,tolylenediamine, xylylenediamine, dianiline methane, ditoluidinemethane,bis(aniline), bis(toluidine), piperazine, and mixtures thereof.
 11. Thegrease composition of claim 1 wherein, when used under high temperatureconditions, high temperature performance in accordance with DIN 51821(FAG FE9) is improved, as compared to high temperature performanceachieved using a grease composition containing other than said polyureathickener.
 12. The grease composition of claim 1 wherein structuralstability and resistance to breaking down is improved when tested underhigh temperature conditions in accordance with DIN 51821 (FAG FE9), ascompared to structural stability and resistance to breaking downachieved using a grease composition containing other than said polyureathickener.
 13. The grease composition of claim 1 wherein, when testedusing a Mini-Traction Machine (MTM) at 100° C., 1.0 GPa, 50% slide/rollratio (SRR), and 3.0 m/s-0 m/s, coefficient of friction is improved, ascompared to coefficient of friction achieved using a grease compositioncontaining other than said polyurea thickener.
 14. The greasecomposition of claim 1 wherein the at least one base oil comprises aGroup I, Group II, Group III, Group IV, Group V base oil, andcombinations thereof.
 15. The grease composition of claim 1 furthercomprising at least one performance additive selected from the groupconsisting of an anticorrosive agent or corrosion inhibitor, an extremepressure additive, an antiwear agent, a pour point depressants, anantioxidant or oxidation inhibitor, a rust inhibitor, a metaldeactivator, a dispersant, a demulsifier, a dye or colorant/chromophoricagent, a seal compatibility agent, a friction modifier, a viscositymodifier/improver, a viscosity index improver, and combinations thereof.16. The grease composition of claim 1 wherein the at least one base oilis present in an amount of from 50 to 95 weight percent, and the atleast one polyurea thickener is present in an amount of from 0.5 to 20weight percent, based on the total weight of the grease composition. 17.A method of preparing a grease composition comprising mixing at leastone base oil, and at least one polyurea thickener; wherein said at leastone polyurea thickener is prepared by reacting an isocyanate-terminatedprepolymer with at least one amine under reaction conditions sufficientto prepare said at least one polyurea thickener; and wherein saidisocyanate-terminated prepolymer is prepared by reacting apolyisocyanate with a polyol, at an NCO/OH equivalent ratio of 1.05:1 to10:1, under reaction conditions sufficient to prepare saidisocyanate-terminated prepolymer.
 18. The method of claim 17 whereinsaid isocyanate-terminated prepolymer has an isocyanate content of 0.5to 40 weight percent, based on the weight of the isocyanate-terminatedprepolymer after reaction.
 19. The method of claim 17 wherein thepolyisocyanate is selected from the group consisting of 2,4-toluenediisocyanate (TDI); 2,6-toluene diisocyanate (TDI);4,4′-diisocyanatodiphenylmethane (MDI); p-phenylene diisocyanate (PPDI);diphenyl-4,4′-diisocyanate; dibenzyl-4,4′-diisocyanate;stilbene-4,4′-diisocyanate; benzophenone-4,4′-diisocyanate; 1,3- and1,4-xylene diisocyanate; and mixtures thereof.
 20. The method of claim17 wherein the polyisocyanate is selected from the group consisting of1,6-hexamethylene diisocyanate (HDI); 1,3-cyclohexyl diisocyanate;1,4-cyclohexyl diisocyanate (CHDI); saturated diphenylmethanediisocyanate H(12)MDI; bis{4-isocyanatocyclohexyl}methane;4,4′-methylene dicyclohexyl diisocyanate; 4,4-methylene bis(dicyclohexyl)diisocyanate; methylene dicyclohexyl diisocyanate;methylene bis (4-cyclohexylene isocyanate); saturated methylene diphenyldiisocyanate; saturated methyl diphenyl diisocyanate; isophoronediisocyanate (IPDI); hexamethylene diisocyanate (HDI);2,2,4-trimethyl-1,6-hexamethylene diisocyanate2,4,4-trimethyl-1,6-hexamethylene diisocyanate; dodecamethylenediisocyanate; 1,4-diisocyanatocyclohexane;1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane (IPDI); 2,4′-and/or 4,4′-diisocyanato-dicyclohexyl methane; 2,4-diisocyanato-diphenylmethane; 4,4′-diisocyanato-diphenyl methane; 2,4-diisocyanatotoluene;2,6-diisocyanatotoluene; and mixtures of these isomers with their higherhomologues.
 21. The method of claim 17 wherein the polyisocyanate isselected from the group consisting of hexamethylene diisocyanate (HDI);2,2,4-trimethyl-1,6-hexamethylene diisocyanates;2,4,4-trimethyl-1,6-hexamethylene diisocyanate; dodecamethylenediisocyanate; 1,4-diisocyanatocyclohexane;1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane;2,4′-diisocyanato-dicyclohexyl methane; 4,4′-diisocyanato-dicyclohexylmethane; 2,4-diisocyanato-diphenyl methane; 4,4′-diisocyanato-diphenyl2,4-diisocyanatotoluene; 2,6-diisocyanatotoluene; and any mixtures ofthese compounds and their higher homologues.
 22. The method of claim 17wherein the polyol is selected from the group consisting of polyesterpolyols, polycaprolactone polyols, and polyether polyols.
 23. The methodof claim 17 wherein the polyol is selected from the group consisting ofpolyester polyols, polycaprolactone polyols, polyether polyols,polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxypolyacrylates, polyhydroxy polyester amides and polyhydroxypolythioethers or mixtures thereof; wherein said polyols have at leasttwo hydroxyl groups per molecule and have a hydroxyl group content of0.5 to 20 weight percent.
 24. The method of claim 17 wherein the polyolis selected from the group consisting of polyester polyols,polycaprolactone polyols, polyether polyols, polytetramethylene etherglycol, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxypolyacrylates, polyhydroxy polyester amides and polyhydroxypolythioethers, or mixtures thereof.
 25. The method of claim 17 whereinthe isocyanate-terminated prepolymer is selected from the groupconsisting of TDI-ether, TDI-ester, TDI-lactone, MDI-ether, MDI-ester,MDI-lactone, H(12)MDI-ether, H(12)MDI-ester, H(12)MDI-lactone,HDI-ether, HDI-ester, HDI-lactone, IPDI-ether, IPDI-ester, IPDI-lactone,PPDI-ether, PPDI-ester, PPDI-lactone, and mixtures thereof.
 26. Themethod of claim 17 wherein the amine is selected from the groupconsisting of pentylamine, hexylamine, heptylamine, octylamine,decylamine, dodecylamine, tetradecylamine, hexadecylamine,octadecylamine, eicosylamine, dodecenylamine, hexadecenylamine,octadecenylamine, octadecadienylamine, abietylamine, aniline, toluidine,naphthylamine, cumylamine, bomylamine, fenchylamine, tertiary butylaniline, benzylamine, β-phenethylamine, stearylamine, laurylamine,palmitylamine, oleylamine, petroselinylamine, linoleylamine,linolenylamine, eleostearylamine, cyclohexylamine, primary tallow amine,ethylenediamine, propanediamine, butanediamine, hexanediamine,dodecanediamine, octanediamine, hexadecanediamine, cyclohexanediamine,cyclooctanediamine, phenylenediamine, tolylenediamine, xylylenediamine,dianiline methane, ditoluidinemethane, bis(aniline), bis(toluidine),piperazine, and mixtures thereof.
 27. The method of claim 17 wherein,when used under high temperature conditions, high temperatureperformance in accordance with DIN 51821 (FAG FE9) is improved, ascompared to high temperature performance achieved using a greasecomposition containing other than said polyurea thickener.
 28. Themethod of claim 17 wherein structural stability and resistance tobreaking down is improved when tested under high temperature conditionsin accordance with DIN 51821 (FAG FE9), as compared to structuralstability and resistance to breaking down achieved using a greasecomposition containing other than said polyurea thickener.
 29. Themethod of claim 17 wherein, when tested using a Mini-Traction Machine(MTM) at 100° C., 1.0 GPa, 50% slide/roll ratio (SRR), and 3.0 m/s-0m/s, coefficient of friction is improved, as compared to coefficient offriction achieved using a grease composition containing other than saidpolyurea thickener.
 30. The method of claim 17 wherein the at least onebase oil comprises a Group I, Group II, Group III, Group IV, Group Vbase oil, and combinations thereof.
 31. The method of claim 17 furthercomprising mixing at least one performance additive selected from thegroup consisting of an anticorrosive agent or corrosion inhibitor, anextreme pressure additive, an antiwear agent, a pour point depressants,an antioxidant or oxidation inhibitor, a rust inhibitor, a metaldeactivator, a dispersant, a demulsifier, a dye or colorant/chromophoricagent, a seal compatibility agent, a friction modifier, a viscositymodifier/improver, a viscosity index improver, and combinations thereof.32. The method of claim 17 wherein, in the grease composition, the atleast one base oil is present in an amount of from 50 to 95 weightpercent, and the at least one polyurea thickener is present in an amountof from 0.5 to 20 weight percent, based on the total weight of thegrease composition.
 33. A method for improving high temperatureperformance of a grease composition in a mechanical component lubricatedwith the grease composition, said method comprising using a greasecomposition comprising: at least one base oil; and at least one polyureathickener; wherein said at least one polyurea thickener is prepared byreacting an isocyanate-terminated prepolymer with at least one amineunder reaction conditions sufficient to prepare said at least onepolyurea thickener; and wherein said isocyanate-terminated prepolymer isprepared by reacting a polyisocyanate with a polyol, at an NCO/OHequivalent ratio of 1.05:1 to 10:1, under reaction conditions sufficientto prepare said isocyanate-terminated prepolymer.
 34. The method ofclaim 33 wherein said isocyanate-terminated prepolymer has an isocyanatecontent of 0.5 to 40 weight percent, based on the weight of theisocyanate-terminated prepolymer after reaction.
 35. The method of claim33 wherein the polyisocyanate is selected from the group consisting of2,4-toluene diisocyanate (TDI); 2,6-toluene diisocyanate (TDI);4,4′-diisocyanatodiphenylmethane (MDI); p-phenylene diisocyanate (PPDI);diphenyl-4,4′-diisocyanate; dibenzyl-4,4′-diisocyanate;stilbene-4,4′-diisocyanate; benzophenone-4,4′-diisocyanate; 1,3- and1,4-xylene diisocyanate; and mixtures thereof.
 36. The method of claim33 wherein the polyisocyanate is selected from the group consisting of1,6-hexamethylene diisocyanate (HDI); 1,3-cyclohexyl diisocyanate;1,4-cyclohexyl diisocyanate (CHDI); saturated diphenylmethanediisocyanate H(12)MDI; bis{4-isocyanatocyclohexyl}methane;4,4′-methylene dicyclohexyl diisocyanate; 4,4-methylene bis(dicyclohexyl)diisocyanate; methylene dicyclohexyl diisocyanate;methylene bis (4-cyclohexylene isocyanate); saturated methylene diphenyldiisocyanate; saturated methyl diphenyl diisocyanate; isophoronediisocyanate (IPDI); hexamethylene diisocyanate (HDI);2,2,4-trimethyl-1,6-hexamethylene diisocyanate2,4,4-trimethyl-1,6-hexamethylene diisocyanate; dodecamethylenediisocyanate; 1,4-diisocyanatocyclohexane;1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane (IPDI); 2,4′-and/or 4,4′-diisocyanato-dicyclohexyl methane; 2,4-diisocyanato-diphenylmethane; 4,4′-diisocyanato-diphenyl methane; 2,4-diisocyanatotoluene;2,6-diisocyanatotoluene; and mixtures of these isomers with their higherhomologues.
 37. The method of claim 33 wherein the polyisocyanate isselected from the group consisting of hexamethylene diisocyanate (HDI);2,2,4-trimethyl-1,6-hexamethylene diisocyanates;2,4,4-trimethyl-1,6-hexamethylene diisocyanate; dodecamethylenediisocyanate; 1,4-diisocyanatocyclohexane;1-isocyanato-3,3,5-trimethy-5-isocyanatomethylcyclohexane;2,4′-diisocyanato-dicyclohexyl methane; 4,4′-diisocyanato-dicyclohexylmethane; 2,4-diisocyanato-diphenyl methane; 4,4′-diisocyanato-diphenyl2,4-diisocyanatotoluene; 2,6-diisocyanatotoluene; and any mixtures ofthese compounds and their higher homologues.
 38. The method of claim 33wherein the polyol is selected from the group consisting of polyesterpolyols, polycaprolactone polyols, and polyether polyols.
 39. The methodof claim 33 wherein the polyol is selected from the group consisting ofpolyester polyols, polycaprolactone polyols, polyether polyols,polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxypolyacrylates, polyhydroxy polyester amides and polyhydroxypolythioethers or mixtures thereof; wherein said polyols have at leasttwo hydroxyl groups per molecule and have a hydroxyl group content of0.5 to 20 weight percent.
 40. The method of claim 33 wherein the polyolis selected from the group consisting of polyester polyols,polycaprolactone polyols, polyether polyols, polytetramethylene etherglycol, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxypolyacrylates, polyhydroxy polyester amides and polyhydroxypolythioethers, or mixtures thereof.
 41. The method of claim 33 whereinthe isocyanate-terminated prepolymer is selected from the groupconsisting of TDI-ether, TDI-ester, TDI-lactone, MDI-ether, MDI-ester,MDI-lactone, H(12)MDI-ether, H(12)MDI-ester, H(12)MDI-lactone,HDI-ether, HDI-ester, HDI-lactone, IPDI-ether, IPDI-ester, IPDI-lactone,PPDI-ether, PPDI-ester, PPDI-lactone, and mixtures thereof.
 42. Themethod of claim 33 wherein the amine is selected from the groupconsisting of pentylamine, hexylamine, heptylamine, octylamine,decylamine, dodecylamine, tetradecylamine, hexadecylamine,octadecylamine, eicosylamine, dodecenylamine, hexadecenylamine,octadecenylamine, octadecadienylamine, abietylamine, aniline, toluidine,naphthylamine, cumylamine, bomylamine, fenchylamine, tertiary butylaniline, benzylamine, β-phenethylamine, stearylamine, laurylamine,palmitylamine, oleylamine, petroselinylamine, linoleylamine,linolenylamine, eleostearylamine, cyclohexylamine, primary tallow amine,ethylenediamine, propanediamine, butanediamine, hexanediamine,dodecanediamine, octanediamine, hexadecanediamine, cyclohexanediamine,cyclooctanediamine, phenylenediamine, tolylenediamine, xylylenediamine,dianiline methane, ditoluidinemethane, bis(aniline), bis(toluidine),piperazine, and mixtures thereof.
 43. The method of claim 33 wherein,when said grease composition is used under high temperature conditions,high temperature performance in accordance with DIN 51821 (FAG FE9) isimproved, as compared to high temperature performance achieved using agrease composition containing other than said polyurea thickener. 44.The method of claim 33 wherein structural stability and resistance tobreaking down of said grease composition is improved when tested underhigh temperature conditions in accordance with DIN 51821 (FAG FE9), ascompared to structural stability and resistance to breaking downachieved using a grease composition containing other than said polyureathickener.
 45. The method of claim 33 wherein, when said greasecomposition is tested using a Mini-Traction Machine (MTM) at 100° C.,1.0 GPa, 50% slide/roll ratio (SRR), and 3.0 m/s-0 m/s, coefficient offriction is improved, as compared to coefficient of friction achievedusing a grease composition containing other than said polyureathickener.
 46. The method of claim 33 wherein the at least one base oilcomprises a Group I, Group II, Group III, Group IV, Group V base oil,and combinations thereof.
 47. The method of claim 33 further comprisingat least one performance additive selected from the group consisting ofan anticorrosive agent or corrosion inhibitor, an extreme pressureadditive, an antiwear agent, a pour point depressants, an antioxidant oroxidation inhibitor, a rust inhibitor, a metal deactivator, adispersant, a demulsifier, a dye or colorant/chromophoric agent, a sealcompatibility agent, a friction modifier, a viscosity modifier/improver,a viscosity index improver, and combinations thereof.
 48. The method ofclaim 33 wherein, in the grease composition, the at least one base oilis present in an amount of from 50 to 95 weight percent, and the atleast one polyurea thickener is present in an amount of from 0.5 to 20weight percent, based on the total weight of the grease composition.